Harrison, who has previously worked at Millwall, Crystal Palace, Wolves, Preston and Aston Villa, has signed a two-year contract.
Harrison was Coleman's number one target to take over coaching duties at the club following the decision to part company with long-time number two Steve Kean.
"Steve has a lot of experience in the Premier League and at international level. He has spent a long time coaching at the very top division and is massively respected in the game," said Coleman.
"He is exactly the right person for me, in terms of where my career is now, and he is the right person to help us take Coventry City to the next level."
Harrison served the England national team as a coach under Graham Taylor and most recently spent over seven years at Middlesbrough under Steve McClaren and Gareth Southgate.