The news broke a day after Pierce confirmed he would be stepping down as the head coach at Long Beach Poly High.
Pierce, 39, will work alongside new head man Herm Edwards in Tempe. The two have worked together at ESPN since 2010.
"Antonio has not only competed at the highest level of football as a linebacker himself in the NFL for nearly a decade, but he has also coached at the highest level of high school football in his time at Long Beach Poly,” Edwards said in a statement. “He will be a valuable addition to our staff and someone we expect to immediately have an impact on our program."
Despite going undrafted out of Arizona in 2001, Pierce spent nine seasons in the NFL and is most known for his five-year stint with the New York Giants, which included a Pro Bowl appearance in 2006 and a Super Bowl XLII ring in 2007.
He retired in 2010 and became Long Beach Poly’s head coach in 2014.
Pierce spent the 2000 season with the Wildcats after transferring in from Mount San Antonio College. Pierce tallied three sacks, 77 tackles (10 for loss), two forced fumbles, one interception, and one blocked kick in his lone year in Tucson.
Arizona has an ASU alum on its coaching staff in defensive line coach Vince Amey.