After failing to test Toulouse goalkeeper Baptiste Reynet with seven attempts on goal, Marseille found the breakthrough when defender Kelvin Amian Adou was judged to have handled by ball from striker Valere Germain's header inside the box.
Referee Ruddy Buquet did not award the penalty initially, only for the Video Assistant Referee (VAR) to alert him that the decision needed to be reviewed on the pitch-side monitor.
Payet stepped up to slot the penalty in the bottom corner before returning from the halftime break to give his team a two-goal cushion.
Substitute Bouna Sarr made a darting run from the right wing only to smash his effort at the goalkeeper, leaving Payet to coolly curve the rebound in with his right foot.
A deft chipped pass from midfielder Morgan Sanson found Germain who added a third goal with a composed finish.
Last season's club top scorer Florian Thauvin, who only recently returned from a successful World Cup campaign with France, added gloss to the scoreline with a goal from close range after a well-directed cross from full back Jordan Amavi.
Toulouse, who needed a playoff win to preserve their top-flight status last season, struggled to create chances throughout the match as they finished with just one effort on target.
Marseille's dazzling display indicates they have the tools to challenge for the top-three places this season, having missed out on a Champions League spot by just one point last term.
(Reporting by Hardik Vyas in Bengaluru, editing by Pritha Sarkar)
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