Forwards Darren Haydar, Andre Deveaux and Kip Brennan and defensemen Arturs Kulda and Noah Welch scored for Chicago (32-24-3-4).
Peoria (34-23-2-3) sealed the win with a power-play goal with 10 seconds left in overtime, when defenseman Mark Cundari took a feed in the slot and cranked a shot past Chicago goaltender Chris Carrozzi.
Center TJ Hensick opened scoring for the Rivermen 54 seconds into the game when he gathered the puck out of the air, settled it down and flung it past Carrozzi.
Peoria brought their lead to 2-0 when defenseman Jake Gannon took a shot that deflected off a Wolves player and into the net, 8:42 into the first frame.
Rivermen center Brett Sonne gave Peoria a 3-0 lead when he collected a rebound off of Carrozzi’s pads and fired it into the empty side of the net, 16:17 into the opening frame.
Chicago got on the board with one second left in the opening frame, 3-1, when Haydar streaked in a pushed a rebound past Peoria netminder Jake Allen.
The Wolves brought the score to 3-2, 1:12 into the second period when the puck flew off Allen and dropped in the paint, allowing Deveaux to pop it into the back of the net.
The Wolves tied the score, 3-3, 4:43 into the second period after left wing Adam Huxley fed the puck to Brennan, who ripped a shot past Allen.
Chicago pulled ahead, 4-3, two minutes later when Kulda fired a blast from the blueline that bounced off of the far post and into the net.
Peoria responded to tie the score, 4-4, halfway through the second frame. Defenseman Ian Cole redirected the puck at the doorstep, beating Carrozzi, glove side.
Carrozzi (0-1-0) stopped 21 shots in his American Hockey League debut.
The Wolves took the lead for the second time, 5-4, 13:22 into the third period when Welch roofed a blast past Allen from the top of the left faceoff circle.
Allen (19-13-2) made 25 saves for Peoria.
Cole knotted the score for the third time, 5-5, with 3:46 remaining in regulation when he fired a shot through traffic in front of the net to send the game to overtime.
The Wolves face the Milwaukee Admirals in an Amtrak Rivalry matchup at the Allstate Arena on Friday at 7:30 p.m.
Chicago 1 3 1 0 -- 5
Peoria 3 1 1 1 -- 6
First Period---1, Peoria, Hensick 18 (Nesbitt, Spina), 0:54; 2, Peoria, Gannon 1 (Sonne), 8:42; 3, Peoria, Sonne 4 (Peluso, Riley), 16:17; 4, Chicago, Haydar 23 (Miller, Esposito), 19:59. Penalties---Huxley, Chicago (fighting), 4:23; Riley, Peoria (fighting), 4:23; Brennan, Chicago (fighting), 4:24; Peluso, Peoria (fighting), 4:24; Garbutt, Chicago (elbowing), 6:19; Hensick, Peoria (slashing), 17:20.
Second Period---5, Chicago, Deaveaux 18 (Machacek, Esposito), 1:12; 6, Chicago, Brennan 1 (Huxley), 4:43; 7, Chicago, Kulda 3 (unassisted), 6:40; 8, Peoria, Cole 4 (Evans, Hensick), 10:05. Penalties---Scatchard, Peoria (tripping), 7:05; Cundari, Peoria (delay of game), 10:24; Pettersson, Chicago (holding), 16:49.
Third Period---9, Chicago, Welch 2 (Garbutt), 13:22; 10, Peoria, Cole 5 (Hensick, Nesbitt), 16:14. Penalties---Evans, Peoria (hooking), 10:43.
Overtime---11, Peoria, Cundari 8 (Oystrick, Allen), 4:50 pp. Penalties---Garbutt, Chicago (hooking), 0:28; Mink, Peoria (hooking), 2:02; Bench, Chicago (too many men), 3:36.
Shots on goal---Chicago: 4-11-14-1--30. Peoria: 9-6-9-3--27. Power plays---Chicago: 0-5. Peoria: 1-4. Goalies--Chicago, Carrozzi (21-27). Peoria, Allen (25-30). A---3,414. Referee---Joe Sullivan. Linesmen---Mike Hamilton and Peter Cichy.