An ECB level three qualified coach, Dobson, 39, is currently in charge of the Super 4s Emeralds team in the premier domestic women's competition.
Having played for Kent and coached Kent Academy, Dobson will quit his position as PE teacher in Canterbury.
Dobson succeeds Richard Bates, who guided England to four successive series wins in his four years as coach.
England's women won the 2005 Women's Ashes in that time, and former Australia pace bowler Cathryn Fitzpatrick also applied to take on the role.
But Dobson won the nod, and he said: "I am absolutely delighted and very excited at the prospect of working with our top women players."
ECB executive director for Women's Cricket, Gill McConway, said: "This is a very exciting time for women's cricket in England.
"With Mark, we get a completely different style from a very enthusiastic individual who expects strong work ethics.
"He has an amazing ability to turn training sessions into high levels of entertainment through his creative and innovative coaching styles."
England captain Charlotte Edwards added: "I'm delighted Mark has been appointed in the role of head coach. He is one of the most inspiring coaches within women's cricket with loads of new and exciting ideas.
"I'm really looking forward to working with him in the forthcoming series against New Zealand (starting 12 August), and looking ahead to the Ashes next year and the World Cup in 2009.
"It's a fantastic appointment and we're all genuinely excited about it."