Benfica were 4-1 winners against Al Nassr on Thursday night, with the Saudi Pro League side heavily defeated by a European side yet again.
Di Maria, who last played for Benfica in 2010, sealed a return to the club at the beginning of the month after one season at Juventus.
The Portuguese champions are gearing up to defend their Primeira Liga title with a series of pre-season friendlies.
Southampton and FC Basel had already been defeated before they faced Al Nassr at Estadio Algarve.
Di Maria made his first appearance back at the club, also scoring, and was on hand to get one over his old pal Ronaldo.
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With Benfica leading 3-1 before half-time, the Argentinian received the ball with his Portuguese opponent rushing towards him.
However, Di Maria evaded the five-time Ballon d'Or winner by delightfully flicking the ball over his head.
Ronaldo still tried to win back possession but could only muster a foul on the winger as he and Al Nassr went on to taste defeat.
It's the second time this week that European opposition have proved too much for the Saudi side after Celta Vigo's 5-0 win on Monday.
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Despite such a result, Ronaldo still insisted that the European leagues have diminished in quality.
"I'm 100 per cent sure I won't return to any European club. I'm 38 years old," he said.
"European football has lost a lot of quality. The only valid one and still doing good is the [English] Premier League. They're way ahead of all the other leagues."
Al Nassr could fall to further defeats though as they prepare for pre-season friendlies against Paris Saint-Germain and Inter Milan.