In the lead up to a live broadcast of the Take That singer's 'Take The Crown' sell-out concert at London's O2 on November 24, the broadcaster has planned several shows.
When Robbie Met James sees Williams interviewed by comedian and actor James Corden, where the pair will discuss music, love and fatherhood.
Williams said: "A proper grilling with my friend James, how could I resist?"
The interview will feature interspersed footage from recent intimate gigs in Leeds, Glasgow and Southend that Williams previously played in 1997, where Corden was in attendance.
Head of entertainment for Sky Phil Edgar Jones said: "Robbie Williams is undoubtedly one of the UK's biggest and best loved entertainers and we are absolutely thrilled to be bringing Sky Customers his spectacular new show.
"That plus James Corden spending some quality time with Robbie makes this a weekend treat not to be missed."
When Robbie Met James executive producer Ben Winston added: "Robbie is an icon of music and a hero to so many generations.
"So to get such amazing access to him at an incredibly exciting time in his career is brilliant. Fulwell 73 are so pleased to be able to make such a memorable programme for Sky1."
Watch Robbie Williams's video for 'Candy' below: