The romantic comedy drama explores the lives, loves and loathes of three couples who are all at different stages of their relationships.
Little will be joined in the production by Amanda Abbington, Lucy Davis, Shaun Dooley, Dean Lennox Kelly and Miranda Raison.
He will play Clint, a serial womaniser and brother of Kelly's character. His single life is challenged when he meets Abbey (Raison), a beautiful model.
"Married, Single, Other is a fantastic mix of laugh out loud humour, high emotion and true romance brought to the screen by a wonderful ensemble cast," said ITV1's director of drama Laura Mackie.
Filming for the six-part series is due to begin this month.