Pioli has previously worked for the New England Patriots, New York Jets and most recently the Kansas City Chiefs, where he left his role as general manager after four years in early 2013.
Having spent the past season broadcasting, Pioli will work under Thomas Dimitroff, whom he worked alongside at the Patriots for six years until 2007.
Dimitroff told the Falcons' official website: "Scott is one of the most respected and adept talent evaluators in the NFL and has been a member of three Super Bowl Championship teams.
"We have worked together well in the past and been friends for more than 20 years. We have had the opportunity to experience a lot of success together, and I am very pleased that he has agreed to join our personnel team so we can work together again.
"We have made the commitment to improve every aspect of our organisation this off-season, and with the addition of Scott to our personnel department, we have taken an important step to enhance our scouting staff."
Pioli will begin in his new position on February 3, once the season is officially over and he is released from his contracts with NBC Sports Network and SiriusXM Radio.