Liberal Democrat challenger Sarah Olney, whose party wants a second referendum on Brexit, is hoping the result will shock Downing Street, as the government ploughs on towards the EU exit door.
Olney is running against Zac Goldsmith, who held the seat for Prime Minister Theresa May's Conservative Party but quit in protest after the government backed expanding the nearby Heathrow Airport.
He is now standing as an independent candidate.
"That's really alarmed and upset people and they want to use this opportunity to send a message."
In the June referendum on Britain's membership in the European Union, 52 percent nationwide voted to leave.
But in the well-heeled borough of Richmond in southwest London, 69 percent voted to remain in the bloc, the 19th highest of 326 voting areas.
The 82 per cent turnout, one of the highest in the UK, showed it was an issue locals felt passionate about.
"The things people want to talk about in this campaign are things we've had a very clear position on," said Olney, meeting commuters outside Richmond railway station.
The 39-year-old accountant only joined the Lib Dems last year and was rapidly selected as their next Richmond Park candidate for the House of Commons.
Former Lib Dem leader Paddy Ashdown, 75, said Thursday's vote could "send a message right to the heart of Downing Street".
However, the Lib Dems face a tough task in overturning Goldsmith's majority. Both the Conservative and Brexit-cheerleading UKIP parties are giving him a clear run.
Goldsmith won Richmond from the Lib Dems in 2010 and retained it in the May 2015 general election with 58 percent of the vote.
Bookmakers have Goldsmith as the 1/3 favourite, with Olney 5/2, and then the main opposition Labour candidate at 200/1. Five others are also standing.
He is the son of the late tycoon financier Jimmy Goldsmith, whose high-spending Referendum Party, calling for a vote on UK-EU relations, got the anti-EU bandwagon rolling.
Zac Goldsmith made a bid for London mayor in May but he was beaten by Labour's Sadiq Khan and was criticised for the tone of his campaign, often focusing on Khan's Muslim faith.
AFP sought an interview with Goldsmith but he is focusing on private grassroots campaigning.
And his understated, local approach seems to have won him support around Richmond.
"There's a lot of loyalty to Zac round here," said Jane McCready, 52, who sat enjoying a hot drink overlooking the River Thames.
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