Calderwood has signed a three-year contract with the Scottish side and replace John Hughes who quit the club before the international break.
Calderwood left his post as assistant manager with Newcastle to move to Easter Road.
“I have enjoyed my time at Newcastle United immensely; it is a great club with a great support,” he told the club’s official website.
“However, I have always wanted to be a manager again in my own right and I am therefore delighted to be given this opportunity at another huge club, Hibernian.
“This is a well run, stable club with a wonderful tradition and terrific facilities. I’m looking forward to working with the squad and can’t wait to get started as we prepare for Saturday’s game at Aberdeen.”
Hibernian chairman Rod Petrie said: “Colin has been in the dugout as a manager in nearly 300 matches.
“He also has a wealth of experience as a player and as an assistant manager in the English Premier League.
“He is a winner, having won promotion with three different clubs. He is a leader with real drive and determination to succeed. This makes him an outstanding choice.”