Ashworth brings an end to an eight-year spell at the Hawthorns having been promoted to sporting and technical director at the club back in 2008.
A start date for the new role is yet to be confirmed, but he will be based at the St George's Park facility, home to the FA's new national football training centre.
"I am really pleased and indeed honoured to have been offered the opportunity to join the FA," Ashworth told the FA's official website.
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"Working within the national set-up has always been a life-long ambition.
"To do so at a time when the future of the game in this country has never looked brighter, through the completion of St George’s Park and the Youth Development proposals, is an exciting challenge which I look forward to taking on."
Alex Horne, the FA’s general secretary praised Ashworth's former club West Brom for their handling of the matter before stating that the appointment is the right one when looking at the grassroots game
"We are delighted to welcome Dan to the FA and offer our thanks to West Bromwich Albion for their courtesy throughout this appointment process," he added.
"Dan is highly regarded and hugely respected within the game and we believe securing his services at the FA will give the future of English football, from the grassroots to the elite level, a tremendous boost."
It is believed that Ashworth will not work specifically with either the England senior team or the Under-21s, instead focusing on the nation's elite talent and their development and Sir Trevor Brooking, the FA's Director of Football Development echoed Horne's thoughts on his appointment.
"We are currently enjoying a hugely exciting and important time for football in this country, from the recently approved Youth Development proposals to the completion of the National Football Centre at St George’s Park," he said.
"I am really looking forward to working with Dan, who will play a crucial role as we continue to develop and deliver The FA’s technical development programme and raise standards of coaching."
Ashworth's key responsibilities will be to help clubs produce more English playing talent, manage the FA's coaching workforce, work alongside Brooking with the U16 to U20 sides and help the new women's elite performances unit produce more female players and coaches for the future.