The broadcaster has yet to disclose Thursday’s panel, but Boris Johnson is widely expected to appear to argue the case for a vote to leave.
The televised debate will follow a head to head between Prime Minister David Cameron and Ukip’s Nigel Farage, to be shown on the channel on Tuesday.
Ms Sturgeon said: ‘’I have been invited to take part as SNP leader and First Minister of Scotland, and I want to make the positive, progressive case from a Scottish perspective for remaining in Europe.
‘’But the message about why we believe staying in the EU is better for jobs, workers’ rights, prosperity and security will be one for an audience across the whole of the UK.”
ITV said “senior political figures” from both the leave and remain sides will take part in Thursday’s debate in front of a live studio audience in London.
Energy Secretary Amber Rudd and shadow business secretary Angela Eagle are among those who have been tipped to join Ms Sturgeon in arguing the case to remain in the EU.