Murray took the tennis world by surprise by appointing Mauresmo, a former Australian Open and Wimbledon champion, as his coach after the French Open.
Initially the deal is only for the grass-court season but both are hoping it will extend beyond that.
The partnership did not get off to the best start with Murray's third-round loss to Radek Stepanek at Queen's Club, but their focus from the start will have been Wimbledon.
After ending Britain's 77-year wait for a men's singles winner 12 months ago, all eyes will be on the world number five when he steps out to begin his defence on Monday.
Bartoli is well-placed to judge Mauresmo's capabilities because it was the 34-year-old to whom Bartoli turned last year for help at Wimbledon.
With Mauresmo in her corner, Bartoli went on to become one of the most surprising champions in Wimbledon's long history.
She said: "If Andy's looking for someone who can help him deal with the pressure of defending the title and coming back again to Wimbledon then he hired the perfect person, because Amelie's really someone that is able to take all the stress away and make you feel extremely comfortable.
"I really felt that way when she was coaching me as my Fed Cup captain or as my adviser during Wimbledon. She was able to give me some small but great advice in order to deal with my stress.
"She prepares you for the worst and gives you some advice in order to deal with that, so when you start to face that situation you are ready.
"I really felt she was a tremendous help to me last year, especially in the final and semi-final."
Bartoli expects Murray and Mauresmo to hit it off on a personal level as well, saying: "They're both extremely funny, I think they will joke around a lot.
"Amelie's been in every situation, she's been a player, a coach, on the bench as a Fed Cup captain. She knows really well what she's speaking about."
While Murray was warming up for his Wimbledon defence at Hurlingham on Thursday, Bartoli was stepping out for a public match for the first time since her shock retirement last August.
The unlikely venue was Liverpool Cricket Club, with Bartoli accepting an invitation to play in the Liverpool Hope University International Tennis Tournament.
Football played a big part in Bartoli's decision to accept the invitation. The 29-year-old is a huge fan and is hoping to return later in the year to watch a match at Anfield or Goodison Park.
"Liverpool, soccer, tennis, grass - that's a great combination," she said.
"If you tell me, clay court, Roland Garros, maybe it would be more tricky. But grass, England, Liverpool, that works pretty well. Wimbledon's right around the corner, there's going to be some amazing memories, it's just a great time."
Bartoli has insisted since laying down her racquet little over a month after winning Wimbledon that she has never had any regrets.
She has done some media work but her main post-retirement activity has been launching a fashion business.
Bartoli is currently working on a line of tennis bags, and she said: "I feel extremely lucky that I've been able to realise my dream as a tennis player but I don't like to call myself a retired person, it's just like I've finished the first part of my life and now I'm starting the second part, which is as a fashion designer and creator.
"This is something I really love to do, I want to explore that and I'm working really hard, just like I did on the tennis court.
"I feel like I'm 1,000 in the rankings and I need to become a Wimbledon champion. It's a long way to go. It took me 22 years to fulfil my dream in tennis, I truly hope it won't take me that time in fashion."