Mott, 48 – paid man at Liverpool Road in 1998 – has signed a four-year agreement and is expected to be in place for England's three-match ODI series against The Netherlands in Amsterdam next month.
The ECB's selection panel of Chief Executive Officer Tom Harrison, Managing Director of England's Men's Cricket Rob Key, Strategic Adviser Andrew Strauss and Performance Director Mo Bobat unanimously agreed that he was the standout candidate for the role during the competitive interview process.
Mott has led the Australian Women's Team since 2015 and during his seven years in charge has overseen one of the world's best winning records across international sport. Under his leadership, Australia Women have won consecutive ICC T20 World Cups, this year's ICC Women's 50-Over World Cup and are undefeated in four Ashes series. Mott has also helped Australia win 26 consecutive one-day internationals, a record in either the men's or women's game.
Before taking up his post with Australia women in 2015, Mott worked as Head Coach of New South Wales - leading them to victory in the Champions League T20 tournament in 2009 - and then coached Glamorgan, reaching the final of the Yorkshire Bank 40 in 2013, before working as a consultant for Ireland during the 2015 ICC Men's World Cup.
Commenting on the appointment of Mott, Managing Director of England's Men's Cricket Rob Key, said: "It is a real privilege to be able to announce Mathew Mott as the Head Coach of our men's white-ball team. He has had an incredible coaching journey with so many varied experiences that have brought him to this point where he was outstanding in the interview process and the perfect fit for our white-ball teams.
"We are lucky to be able to appoint a Head Coach that has not only been involved in international cricket for the last few years but he has also worked in franchise cricket around the world. More importantly, what he has done with the Australian Women's team is what will be asked of him to achieve for our men's white-ball sides.
"I'm confident that in Eoin Morgan and Matthew Mott, we have a formidable partnership that can push for more trophies in the coming years and that Matthew will be able to oversee any transition that team will go through in the future.
"Furthermore, Matthew will also help us invest in English coaches getting them as much experience as possible over the next few years."
Mott, who hit 785 runs in 1998 for the West Enders, taking 34 wickets, added: "I am delighted to accept the opportunity to take this white-ball role with England. Whilst I am Australian, I have deep connections, and several of my closest friends are in the UK, having spent considerable time in Scotland, Wales and England, both as a player and coach.
"When this role became available, I was attracted by the chance to work with such an established and successful team under the astute leadership of Eoin Morgan and now Rob Key, whom I have always admired as an excellent cricket mind.
"The idea of the split roles and the chance to work alongside Brendon McCullum in his red-ball role is an opportunity that I am incredibly enthusiastic about and certainly provides the right balance for my family as we embark on this exciting journey.
"It was always going to take something special to leave the role that I have loved for the past seven years with the Australian Women's team. However, I genuinely believe that the time is right to play a role in helping the England Men's ODI and T20 group continue to evolve as one of the best teams in the world.
"I am fully aware that this team has been functioning well and part of my initial plan is to work with the playing group and support staff on how we can firstly maintain, then enhance, the success they have started to build over the past few years.
"Since the excitement of accepting this role, I, like many people around the world, have been trying to come to terms with the tragic loss of my great mate Andrew Symonds. The support of his beautiful family and close friends in the coming days will be vitally important, so I respectfully request some time to process his passing and the immense loss before making any further comment on the role at this stage."