Lucas and Adam start their journey in the Riverina in NSW where they meet Jim Crocker, a collector and yard owner who specialises in Furphy Water Carts. Furphys were used in the days before irrigation to transport water around farms and on the battlefields of World War I. Next stop is the Magpie's Nest Restaurant in Wagga where they meet Chris Whyte. Chris is a chef and a long time collector. Chris takes the Pickers to the attic above the restaurant, where they find a Picker's paradise. It's not a huge area, but there is plenty of scope. Chris then suggests the Pickers' visit his father Jim, and his uncles, Jackie and “Skinny” (AKA Terry) who have a huge yard on the other side of town. The Whyte Brothers' yard turns out to be a treasure trove and the Pickers' find plenty of bargains. Among the purchases is an old-style bellows camera, which can be mounted on a steel rail. At least, Lucas thinks it's a camera. He's not completely sure, but buys it on spec for $80. Finally the Pickers' travel to an old family farm with an abandoned farm house that has been empty since 1981, when the owner died. There they meet Joan, who runs the farm and who gives them permission to pick through the old homestead, which is still full of furniture, books and kitchen items.

Deep in the hills of Northern New South Wales Lucas and Adam meet a guy who calls himself Mad Dog, and they approach the assignment with trepidation. Mad Dog turns out to be a friendly character, who initially shows them his collection under his house. Lucas and Adam are a little disappointed at coming so far to see so little, then Mad Dog takes them to the back of his property to his shed, which is a huge structure filled to the brim and a massive pick is underway. Next stop is Warwick and Gwenda, who have been collecting together since their honeymoon 49 years ago. Warwick and Gwenda collect literally anything and everything including an extensive collection of Australian phone books and beer cans from every beer producing country in the world. Their collection is catalogued and housed in a huge 2-storey shed. In the New South Wales Snowy Mountains, the "Pickers" visit passionate car collector Mick Ambrose, who has car bodies and parts strewn across 25 acres outside town. The "Pickers" buy some car pieces from Mick, then go next door to meet Mick's neighbour, Kim who likes to preserve old car bodies and other pieces because he doesn‟t want to see them melted down.

Lucas's day starts well when he spies a pair of unusual bar stools in the kitchen of the motel where they spent the night. Lucas does a deal with the owner, and packs the stools into the truck. The Pickers head up the Murray River in Victoria to meet Mingo, a collector who specialises in FJ Holdens and vintage Indian and Harley Davidson motorcycles. Mingo's wife is sick of the clutter, so he's planning to have a large clearing sale on the site, but he gives the Pickers a preview of his stock. Lucas picks up a 1970 Indian Trail Bike, but is it a real Indian? Or has he done his dough? Back on the road, they meet John, a former antique dealer. John has closed his store and all his stock is spread among two houses side by side in suburban Wagga. As a dealer, John is a skilled negotiator and a hard bargainer, as Adam finds out several times during their visit. Lucas buys a tray of cutlery for $10, but he's fairly sure there are some valuable pieces in there and he‟s going to get a silver expert to value them. Then it's off to a massive storage shed owned by Brian Toole. Brian's family ran an army disposal business for many years, until Brian closed the store and put all the stock in the shed. He stocks huge amounts of military material, along with a number of collectables. Back at Picker HQ, the Silver expert appraises the cutlery Lucas bought from John the antique dealer. What will it be worth?

First stop this week is the gigantic Toowoomba Swap Meet, an annual 3-day event attracting thousands of collectors from across Australia. At the Swap Meet, Lucas and Adam meet James, the self-proclaimed custodian of old bicycles. James invites the boys to see his house. James has had his house raised ten feet to create a huge workshop area underneath, which is full of bikes and bike parts. In the house itself, bikes fill every room, hanging from the ceiling and in a purpose built attic. Next stop is Eddie and Thelma, an elderly couple who keep a huge collection of Australiana and machinery on a property outside town. Eddie's pride and joy is a 1923 Fiat racing car, which he says is worth $1 million. Then it's off to the Northern New South Wales town of Kyogle, to meet Stewart, who runs a movie museum in the town's cinema. Stewart takes Lucas and Adam to see his shed outside town, where he keeps a huge amount of old and rare projection equipment as well as old cars and other collectables.

In Wagga, the Pickers meet Brian, the collector's collector. Brian's collection of Aussie memorabilia has been voted the best in Australia. After admiring his extensive collection, the Pickers convince Brian to show them the space under his house where he keeps even more. Here they manage to convince him to part with some treasured items. The Pickers visit a junk yard on the outskirts of Sydney. Owners Sue and Gary collect anything and everything from garage sales, demolition sites and tips. The Pickers buy quite a bit along the way, before being taken into Gary and Sue's backyard to see their private collection. This is mind-boggling, including a secure vault filled with vintage petrol pumps and other assorted Garagenalia material valued at several million dollars. Finally, in the Hunter Valley of NSW, the Pickers come across Marilyn and Paul, who used to run a small country museum which they closed several months ago and are now trying to sell some stock and Lucas and Adam are only too happy to help them out.

Lucas and Adam take on Tasmania. In the north of the island, they meet Ian, a true Tassie character who refers to himself as a Bower Bird. Ian has an extensive collection just waiting to be picked. Ian sends the Pickers to meet his mate Steve, a self confessed treasure hunter who describes his collection as "organised chaos", strewn around sheds and paddocks across his property. Next stop is train fanatic Howard, who is creating his own railway world in a remote part of Northern Tasmania. Howard's love of trains extends to dressing as a railway conductor and building his own train station on the property. From here, they go on to meet Tassie couple George and Michelle. George is a hoarder, who wants to keep everything so he can fix it up and pass it on to his kids. Michelle is desperate to see some sold so she can have a little more room to move.

In country Victoria, the guys meet local auctioneer Bruce, who is known to the locals as Steptoe. It's the battle of the auctioneers when Bruce goes head to head with Adam and some lively haggling ensues. Then it's off to visit Precis, whose warehouse is full of quality furniture. Precis finds his best stuff by scouring the newspaper ads for deceased estate sales. Lucas enters the holy grail of furniture, but will he find that rare Featherston chair he's been dreaming of? Finally, the guys visit the man cave of Ian, a garage-sale nut who bought a suburban warehouse and yard just to hold his collection of cars and memorabilia. Here, Adam finally finds the piece he has been searching for since he began picking, but what is it?

In outer Melbourne Lucas and Adam come across a truly incredible military collection when they call on John and his son Bill. John has sheds filled with Militaria and yards full of old military vehicles, including a collection of tanks and armoured personnel carriers. On the outskirts of Melbourne Lucas and Adam meet Sandy and Brian, a happy collecting couple who spend all their spare time picking through the bargains at their local opp-shops. Brian says they have been called hoarders, but they prefer to think of themselves as “accumulators”. In a house and garden filled with amazing items, the Pickers' budget takes a beating, but they come away with quite a haul. Then it's off to visit old rockers Rod and Pam, whose back shed has been transformed into a 1950s American diner, complete with juke box. Rod collects rock and roll memorabilia and also has an extensive collection of vintage juke boxes for sale.