Host Paul Martin will bring the BBC weekday programme to the exquisite Painted Hall at The Old Royal Naval College on Saturday, January 30.
Residents can bring along up to three collectables they want to sell which will be scrutinized by the team.
Once they have been given a price, a decision is made about whether the item should go under the hammer at auction a few weeks later.
Everyone who visits the World Heritage Site for the event will be treated to a free valuation regardless.
Presenter Paul Martin said: “I’m looking forward to exploring the Old Royal Naval College and revealing some of the area’s fascinating history to our viewers.
“I hope as many people as possible will come along to see us with their items for valuation.”
The valuation day will run from 9.30am until 4pm.
Meanwhile, items selected will feature at Chiswick Auctions in W3 on Tuesday, February 16.