He admitted to surprise at the appointment, prior to his second-round match tomorrow against Murray, the reigning Wimbledon champion, at the Aegon Championships, in which the Scot is also defending albeit only as the No.3 seed.
Mathieu, 32, saw off the Slovene Aljaz Bedene 7-6, 6-4, to set up his Queen's Club showdown with Murray, and he praised the Wimbledon champion for taking such a bold step. "It's going to be an interesting relationship," said Mathieu. "I didn't hear about it in advance, but they must have thought about it, and talked about it together; I think it can work. She has a lot of experience in the game, and she loves tennis; she always played with passion and I think like Andy as well. Approaching the game and the big event I think she can help him.
"I was surprised, honestly, and I think I'm not the only one. It's the first time this has happened that a woman will train a man. I don't think it's a bad thing, and I think we'll see it more and more. I like the fact Amelie will train Andy because it will bring something new in our sport. She had a great career, she's very professional and very passionate about tennis, and that's the most important thing.
"I'm happy to have a match on grass before playing Andy [who had a bye through the first round]. I'm going to have to turn my mind on to the grass season and it's going to be difficult."
Heather Watson, who has replaced Laura Robson as Britain's No.1 female player, refuses to differentiate between the men's and women's games at world level, and hopes that Murray giving Mauresmo a key role will broaden wider horizons.
"I don't like to separate men and women; I don't view it as any special thing," she said. "She has vast experience as a player and a coach, whether she is a woman or not. She has grand slam titles so if she has the information and knowledge that Andy feels he needs then that's great and I hope it works out for both of them."
Judy Murray, the Great Britain Fed Cup captain, has indicated there is hard work ahead if numbers in the domestic women's game are to be boosted, and plans are under way aimed at setting up programmes tailored to young girls.
While Murray must wait another day to begin his defence of the trophy, his Davis Cup team-mate James Ward accepts he must force an upset against Grigor Dimitrov as he attempts to repeat his 2011 run to the semi-finals.
The British No.3 beat Blaz Rola for the second time in three weeks to set up a match against the No.4 seed. Ward became the first British man in more than 40 years to reach the French Open first round proper when slugging past his Slovenian opponent in a gruelling 12-10 final set on May 23. The 27-year-old defeated him again in straight sets 7-5, 6-4 yesterday, to tee up the Dimitrov match.
"It would be an upset if you look at the rankings no doubt," said Ward. "Probably this would be the best surface for me to face him on. We practised last week though and we know each other pretty well anyway, so I think it will be a good match."
Dan Evans, meanwhile, shrugged off an 88-place world ranking disadvantage to dispatch Jurgen Melzer 6-3, 6-7 (5-7), 7-6 (7-2) but another Briton, Daniel Cox, slipped to a straight-sets defeat to Frenchman Adrian Mannarino.
Elsewhere, the four-time champion Lleyton Hewitt eased past the Spaniard Daniel Gimeno-Traver in straight sets.