The Oprah Winfrey Network have said the 36-year-old will be 'one of many notable celebrities' to appear in the programme's first fortnight.
Rosie's new chat show will be filmed at Chicago's Harpo Studios, which was home to The Oprah Winfrey Show for 25 years.
Earlier this week, O'Donnell revealed that Katy Perry's husband was '100 per cent my celebrity crush'.
She told Access Hollywood: 'I became fascinated with him and I Googled everything he ever did and I fell madly in love - I became obsessed.
She said she had since seen him at an airport and told him: 'I have been marinating in you, I knew this would happen, you are genius.'
The Rosie Show premieres on October 10.