Murray's management team announced in a statement that Mauresmo will initially work with the Scot for his grass-court campaign, which gets under way at Queen's Club this week in the build-up to his defence of the Wimbledon crown.
"I'm excited by the possibilities of the new partnership and Amelie is someone I have always looked up to and admired," Murray wrote on his official website.
"She's faced adversity plenty of times in her career, but was an amazing player and won major titles, including Wimbledon."
But in the end he has gone for former world number one Mauresmo, who was first mooted as a shock candidate after she watched his match against Andrey Golubev at the French Open.
The 27-year-old's decision to hire a woman will be seen by some as a gamble, but Mauresmo, who won Wimbledon in 2006 before retiring in 2009, already has experience of coaching a male player after a spell with compatriot Michael Llodra.
Murray, who was thrashed by Rafael Nadal in the French Open semi-finals, has no doubts about her credentials.
"I have a very strong coaching team already in place, but I think Amelie brings with her experience and tactical expertise and will push us all to improve," he said.
"Everyone I know talks very highly of Amelie, as a person and coach, and I'm convinced that her joining the team will help us push on. I want to win more grand slams.