The Frenchwoman, who won two grand slam singles titles, including Wimbledon, will work initially with Murray for the grass-court season, starting with this week's Aegon Championships in London, where the Scot is the defending champion.
"I obviously worked with my mum [Judy Murray] for a long time and then even for periods when I was 16, 17 years old, so it doesn't feel like a very different thing," Murray said.
"Obviously I wasn't paying my mum so it'll be a little bit different this time around because I'll be employing Amelie. It's exciting, something a bit new for me, a bit fresh, and hopefully it works well."
Mauresmo fills the void created by the departure in March of Ivan Lendl, who helped Murray win his first grand slam title, at the US Open in 2012, and Wimbledon last summer, as well as gold at the London Olympics.
Murray said he had considered a number of potential candidates but is looking forward to working with Mauresmo, who helped Marion Bartoli win Wimbledon last summer.
"I spoke to her a few times on the phone and when I was in Paris I met her before the tournament," Murray said. "We chatted a little bit about it, whether she'd be up for doing it. There was a will from both sides to give it a go and see how it works out. We'll try during the grass-court [season] and hopefully both enjoy it.
"She's obviously a fantastic player. She won Wimbledon, she was world No.1, won the Australian Open.
"Just from speaking to her, she's very calm, she's a good person. I think we will communicate well and that's a very important part of coaching."
Mauresmo said she cannot wait to get started but said the male-female discussion is not important.
"I think he's maybe looking for something different, about emotions and sensitive things," she said.
"But it's not really interesting for me, this part of the story, to be honest. All I'm interested in is to be able to help him in his goals. That's about it. The rest is the story for you to write, I guess."