Experienced striker Guerrero, who was only allowed to play in the tournament after the captains of Peru's World Cup opponents petitioned FIFA to temporarily lift his suspension, made the most of what may have been his final appearance for Los Incas, who finished with three points to add to the many plaudits they have won in Russia.
Their opener would have been worthy of winning any World Cup match, Andre Carrillo volleying Guerrero's weighted cross into the net to beckon forth a cavalcade of emotion from the hordes of Peru fans packing the stands in Sochi.
The talismanic Guerrero, 34, made his mark on the game's biggest stage with his 36th international goal early in the second half, extending his record as the country's all-time leading scorer.
Despite head coach Bert van Marwijk throwing on talented 19-year-old Daniel Arzani and veteran Tim Cahill to try and turn the game, Australia failed to muster a comeback as they finished bottom of Group C.
34y 176d - Peru's Paolo Guerrero (34y 176d) is the third oldest South American player to ever score at the World Cup, after Uruguay’s Obdulio Jacinto Varela (36y 279d) and Argentina’s Martin Palermo (36y 227d). Blanquirroja.#AUSPER #PER #WorldCup pic.twitter.com/MeL8lQcfJe — OptaJoe (@OptaJoe) June 26, 2018
Mile Jedinak was booked for a high boot on Christian Cueva after nine minutes of the first half and Australia looked the better side as they sought to stamp their authority on the game.
But they were rocked by a brilliantly taken Peru goal after 18 minutes when Guerrero broke into the penalty area, cut back onto his right foot and swung a deep cross for Carrillo to lash a volley through Jedinak's legs and into the bottom right corner of Mat Ryan’s net.
Peru then had to soak up some pressure as Tom Rogic beat three defenders on a jinking run into the penalty area after 26 minutes and saw his shot saved by Pedro Gallese, before Mathew Leckie was denied by a last-ditch Anderson Santamaria tackle as he slid in on goal.
The second half was five minutes old when Guerrero struck, hooking the ball into the far corner of the net beyond Ryan's left hand to leave Australia with a sizeable task ahead of them.
They set about it immediately as Jedinak's far-post header was denied by Gallese and Trent Sainsbury fired wide from close range, while substitute Cahill had a volleyed effort blocked in the penalty area.
As the minutes ticked away so too did Australia's hopes of a turnaround; Aziz Behich got in behind the Peru defence and had time and space to pick his spot but instead opted to send a cross beyond the unmarked Cahill.
Edison Flores almost added a third goal on the counter when he crashed a low drive onto the post from the edge of the box in the closing minutes, but the offside flag was raised and there was to be no final flourish for Peru.