Simpson, a seven-time PGA Tour winner who played on three losing Ryder Cups teams in 2012, 2014 and 2018, is the first vice-captain to be appointed by Bradley.
"Webb is someone who I have long admired and respected as a competitor and friend," Bradley, who was announced as captain two weeks ago, said in a news release.
"He possesses a wealth of team golf experience and knows what it takes to win. Webb will be a valuable member of our leadership team and a trusted resource for me as we prepare for Bethpage Black next September."
The 2025 Ryder Cup will mark Simpson's first stint as a vice-captain in the biennial team event. The 38-year-old Charlotte, North Carolina, native played in three, compiling a 4-4-1 career record, including 2-1-0 in fourball matches.
"Competing in three Ryder Cups will forever be among my career highlights," said Simpson, who was also a member of the victorious US teams in the 2011, 2013 and 2019 Presidents Cups.
"I have no doubt that Keegan will be a fantastic captain and a tremendous leader, and could not be more excited to get to work as we seek to reclaim the Ryder Cup at Bethpage Black."
Additional vice-captains will be announced later.
