The Argentina international replaced the injured Neymar in the starting line-up at the Parc des Princes and struck the opening goal in first-half stoppage time.
Di Maria added a second shortly after the interval before Edinson Cavani wrapped up a second 3-0 victory over Marseille in four days, following Sunday's home league win that came at a heavy cost.
PSG announced shortly before kick-off that Neymar, the world's most expensive player, would travel to Brazil for an operation at the end of the week after suffering a hairline fracture of the fifth metatarsal in his right foot.
"We all took the decision together, the club, the player and the Brazilian team doctor," said PSG president Nasser Al-Khelaifi.
"It's a difficult decision but it's the only option we have. We hope to have him back quickly. I can't say when he will return, all will depend on the recovery."
The absence of the 222-million euro ($264 million) Brazilian is a bitter blow to PSG as they attempt to overturn a 3-1 deficit against Real Madrid next Tuesday in the Champions League last 16.
Marseille goalkeeper Steve Mandanda, absent for Sunday's loss, had produced a magnificent save to deny Di Maria minutes earlier but was helpless to keep out the Argentine's shot as it flicked Adil Rami before nestling in the corner.
Poor defending presented the former Real player with his second on 48 minutes, as Aymen Abdennour failed to cut out Yuri Berchiche's left-wing cross and Di Maria turned home via another deflection with the ball creeping past Mandanda.
The holders are joined in the last four of the competition by two third-division clubs -- Les Herbiers and Chambly -- while Lyon visit Caen in Thursday's remaining quarter-final.
Les Herbiers knocked out Ligue 2 outfit Lens in a penalty shootout on Tuesday following a goalless draw in Nantes, with Lassana Doucoure scoring a late winner for Chambly in Wednesday's 1-0 win over top-flight Strasbourg.
Disclaimer: No Business Standard Journalist was involved in creation of this content
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