Trade Union Congress general secretary Frances O'Grady is to take on former Confederation of British Industry leader Digby Jones over the UK's European Union membership in the final days before Britain's referendum.
O'Grady will be joined in the debate by London Mayor Sadiq Khan and Scottish Conservatives leader Ruth Davidson, with the trio all arguing for the Remain camp.
For the Leave campaign, Jones will be joined by Khan's predecessor Boris Johnson, and Labour's Gisela Stuart.
It will be hosted by David Dimbleby, Emily Maitlis and Mishal Husain.
A BBC spokeswoman declined to comment.
The BBC debate will mark the final round of live TV sessions, coming after Johnson and Stuart took part in a contentious debate on ITV last week, where energy secretary Amber Rudd accused Johnson of misleading the British public.
Previous events have also seen Ukip leader Nigel Farage and Prime Minister David Cameron facing bruising sessions on migration.