The former Australian Opals coach impressive CV includes coaching the Opals to win bronze at the Atlanta Olympics in 1996 and to silver in Sydney four years later.
Maher also coached New Zealand to finish eighth at the Athens Olympics - their highest ever international placing, and only last summer took the Chinese team to a fourth place finish in Beijing.
The Australian said: "Taking the GB job was a no-brainer really. Who wouldn't want the opportunity to coach a home nation at the Olympics, in a city I've spent almost no time in? It was an easy decision.
"Certainly the British team will be better. GB has made a lot of effort to improve, that much is clear and now I'm going to try as hard as I can. When it comes down to it you can only do your best and be proud of that."
With a summer free of internationals Maher is focused on getting the girls to recognise the changes they need to make to transform from a domestic team to an international force to be reckoned with.
Appreciating that there will be no quick fix to get Britain up to standard, he told the British Basketball Federation's website: "I haven't seen any of the girls yet. I wouldn't say that's particularly daunting but it's going to be frustrating," Maher continued.
"GB has got to take gigantic steps. There's a difference between domestic basketball and world basketball and that's key. It's little things like emotional advances which they have to make, but this is all part of the learning curve.
"The important thing to remember is that you don't make something happen overnight. I'm not expecting it to be all wonderful to begin with."
When asked what he thought of the appointment, British Basketball Performance Director Chris Spice said: "It goes without saying that to have someone of Tom's calibre commit to us should act as both a vote of confidence to the team but also demonstrate our program's intent.
"Not only does Tom have firsthand experience of helping teams grow and progress, but he has done so with two home nations at an Olympics which we hope will be priceless for us, not just with the women but across the programs."
Maher missed out on the job to lead the Australian Opals to the London Olympics but signed on as head coach of Women’s National Basketball League club the Bulleen Boomers in early April.
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