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But Conservative Theresa May and Labour's Jeremy Corbyn will not take part in the ITV clash, which begins at 20:00 BST.
Lib Dem leader Tim Farron, UKIP's Paul Nuttall, SNP leader Nicola Sturgeon, Plaid Cymru's Leanne Wood and Green Party of England and Wales co-leader Caroline Lucas will take part.
The debate takes place in Salford.
It is the first of several election specials scheduled to take place ahead of the 8 June general election.
Mrs May has said she will not take part in any live debates, and Mr Corbyn has said he will only take part if she does.
ITV has said the invitation to take part remains open to the two leaders until the programme starts, but if they do not show up they will not be "empty chaired" as ITV said the stage will have "the right number of podiums for leaders who attend on the night".
The BBC will hold a Question Time special on 2 June in which Mrs May and Mr Corbyn will face audience questions consecutively.
SNP leader Nicola Sturgeon and Lib Dem Tim Farron will appear in another on 4 June and there will be a live debate featuring senior figures from seven parties on BBC One on 31 May.