Guerin will work with prospects throughout the Penguins' organization after finishing his playing career in Pittsburgh in 2009-'10.
Guerin won two Stanley Cups, one with Pittsburgh, during an 18-year career in which he also played for New Jersey, Edmonton, Boston, Dallas, St. Louis, San Jose and the New York Islanders.
The six-foot-two, 220-pound forward had 429 career goals and 427 assists.
"Billy has only been retired as a player for one year, so he brings a new and very contemporary perspective to the position," Penguins general manager Ray Shero said in a statement. "He is going to be a big asset to our young prospects throughout the organization, and to our staff."