He out-of-contract Bayern Munich star struck the winning goal to leave all four teams on three points and leave it all to play for in the final round
Veteran Claudio Pizarro helped Peru to a priceless 1-0 victory against Venezuela as Ricardo Gareca's men stayed in the hunt for a Copa America quarter-final berth.
Peru were left heartbroken last time out after conceding an injury-time goal in a 2-1 loss to Brazil in their Group C opener on Sunday.
The Peruvians appeared set for another frustrating outing, despite playing against 10 men for over an hour after Venezuela left-back Fernando Amorebieta was sent off for stomping on Paolo Guerrero in the 29th-minute on Thursday.
But 36-year-old Pizarro - a replacement for Jefferson Farfan in the starting line-up - spared Peru blushes with a 72nd-minute winner at Estadio Elias Figueroa Brander in Valparaiso.
Guerrero played in Pizarro, who made no mistake from close range for his 20th international goal - moving him level on Peru's all-time scoring list alongside former Newcastle United midfielder Nolberto Solano.
Peru, Venezuela, Colombia and Brazil are now level on three points heading into the final round of group fixtures.
The best chance of the first half fell to striker Salomon Rondon - the hero for Venezuela in their shock 1-0 win against Colombia - in the sixth minute.
A quickly taken free-kick from Alejandro Guerra on the left wing almost picked out Rondon, who beat the offside trap just outside the six-yard box, but despite getting his outstretched boot to the ball, the Zenit forward was unable to generate enough power to trouble Peru goalkeeper Pedro Gallese.
Neither team generated anything clear-cut from that point in the first 45 minutes, though the match sprung into life approaching the half-hour mark, when referee Raul Orozco issued a straight red card to Amorebieta.
Amorebieta and Guerrero battled for possession on the left wing before the former appeared to stomp on his opponent's knee.
The 30-year-old's dismissal forced Venezuela into an early reshuffle and substitution, with midfielder Ronald Vargas sacrificed in favour of left-back Gabriel Cichero seven minutes before half-time.
Peru controlled proceedings from the restart, though Rondon still proved to be a handful up front as Venezuela played on the counter, almost breaking through on goal five minutes into the second half.
Peru then went close to scoring just past the hour-mark but Guerrero's cross eluded his team-mates inside the penalty area.
They eventually made their numerical advantage count with 18 minutes remaining via Pizarro, who fired powerfully past Alain Baroja, despite the goalkeeper getting a hand to the ball, as Venezuela's stubborn resistance was finally broken.