The programme was presented by Robert Peston, the Political Editor of ITV News, and featured discussions with politicians and public figures on the major news events of the week alongside analysis and social media reaction with Allegra Stratton, the then-National Editor of ITV News.

As a Sunday morning talk show, in contrast to the style of questioning employed by rival programmes like The Andrew Marr Show and Sophy Ridge on Sunday, Peston on Sunday featured a more relaxed, conversational approach to engage and explore the opinions of the political guests.

[4] Episodes were broadcast from Liverpool, Birmingham, Brighton, Manchester and Glasgow during the party conference seasons of 2016 and 2017.

[5] It was confirmed on 5 May 2016 that Chancellor of the Exchequer George Osborne would be one of the studio guests on the launch episode of Peston on Sunday with the first run leading in to and dealing with the immediate aftermath of the EU Referendum.

The fourth run launched on 23 April 2017, the week after Prime Minister Theresa May called a snap general election to be held on Thursday, 8 June 2017.