Heavyweight Pat (HD) Barry, meanwhile, will take on former LSU fullback Shawn (The Savage) Jordan.
The card is set for Winnipeg's MTS Centre on June 15.
Woodley (11-1) is coming off an impressive first-round KO of Jay Hieron, rebounding from a Strikeforce title loss to Nate Marquardt.
Shields (27-6-1 with one no contest) last fought as a middleweight in a UFC 150 win over Ed (Short Fuse) Herman that was ruled a no contest after Shields admitted taking a banned substance. He was suspended for six months and fined US$5,675.
Barry (8-5) knocked out Shane Del Rosario in December. Jordan (14-4) stopped Mike Russow.
Already announced is a light-heavyweight rematch between Mauricio (Shogun) Rua and Antonio Rogerio Nogueira and a heavyweight bout between Soa Palelei and Stipe Miocic.
Interim bantamweight champion Renan Barao will face Eddie Wineland in the main event while Dan Henderson meets former light-heavyweight champion Rashad Evans.
In a lightweight battle, Sam Stout of London, Ont., will take on Isaac Vallie-Flagg.
In other UFC news, the organization returns to Brazil on May 18, as the Jaragua Arena in Jaragua do Sul, Santa Catarina, hosts a televised card UFC. Veteran Vitor (The Phenom) Belfort will fight former Strikeforce middleweight champion Luke Rockhold in the main event.
In the co-main event, former Strikeforce middleweight champion Ronaldo (Jacare) Souza faces Cypriot Constantinos (Costa) Philippou. Canadian Roger Hollet will fight light-heavyweight Fabio Maldonado on the card.
Flyweight Joseph Benavidez will face Darren Uyenoyama on the April 20 televised card in San Jose. And bantamweight Francisco Rivera takes on Hugo Viana.