Barney, a former sailing athlete and coach, worked for the England and Wales Cricket Board before joining GB Hockey as head of talent development in 2013.
He takes over from Danny Kerry, who had been both performance director and interim women's head coach since 2014.
Kerry, who guided Britain's women to Olympic gold in August, said in April he would focus on coaching full-time.
"Our sport is in an amazing place," Barney said.
"After the women's team's success in Rio, we are now presented with a great opportunity."
Ed Barney has been named Great Britain hockey's new performance director - overseeing the men's and women's teams.