Di Carlo will succeed Luigi Del Neri who has become new boss at Juventus.
Di Carlo has signed a two-year contract with Sampdoria.
“The offer from Sampdoria was one I couldn’t refuse,” the new boss told the club’s official website.
“I know I have a lot to do to match the work of Delneri, but I am not fazed by the challenge.
“I wanted to stay at Chievo but when someone offers you the chance to compete in the Champions League, you can’t say no.”