All too often, especially in the minds of fans, ex-players always seem to pop up and find a way to score against their former team.
The 30-year-old Argentine forward used to be first-choice at the Parc des Princes, but with the arrival of Neymar and Kylian Mbappé he was pushed down the pecking order.
Inter Milan and Barcelona were heavily linked with a move for Di María in both the summer and winter transfer windows, with many expecting the Parisians to sell in order to avoid any Financial Fair Play sanctions.
Yet now he and the favourites to win Ligue 1 welcome the Spanish giants to the French capital, hoping he can put his former club to the sword.
PSG lost their Brazilian superstar to a broken bone in his foot at the end of last month. Surgery will be needed, and many believed along with his exit went any chances of a second-leg comeback.
Neymar was disappointing in the fixture at the Santiago Bernabéu, taking a bullish and selfish approach. At times he was trying too hard, ignoring his team-mates and ultimately reducing their chances of putting in a cohesive team performance.
Without the 25-year-old, PSG need to pull together and banish the ghosts of last season’s elimination at the hands of Barcelona. They are good enough to score twice, undoubtedly – on their day, they could do to Cristiano Ronaldo & Co. what they did to Barça at home last year.
Di María will be at the heart of Unai Emery’s planning on Tuesday and it will be a chance for the former Manchester United flop to prove his worth on European football's biggest stage.
He has 17 goals in all competitions this season. Starting with a hat-trick against Sochaux in the Coupe de France at the start of February, he has scored seven in six games and was excellent in PSG’s 3-0 win over Marseille in the same competition.
Scoring twice just three days after they lost Neymar, it was almost like he was firing a warning shot not only to Real, but anyone else vying for his spot in the team.
Mbappé was forced off at half-time during their win over OM, sending the Parisian fans into panic mode, but Unai Emery tried to ease those fears, revealing the 19-year-old French forward would be fine.
“Mbappé trained normally with the squad yesterday. The only player, apart from Neymar, who did not, was Javier Pastore.
“Normally, all players will be ready for tomorrow's match against Madrid, except Neymar.”
Expectations are, after starting Di María with Julian Draxler and Christopher Nkunku on Saturday against Troyes, the Argentine forward will be joined by the former Monaco teenager and Edinson Cavani on Tuesday.
Usually, the youngest of the three has been playing on the right of the three-man attack, but so has Di María.
Di María is deadly coming inside onto his left foot, either whipping in crosses for their No.9 or trying his luck from distance.
He also showed, for his goal against Troyes in the 2-0 win, he can link up through the middle and make those dangerous driving runs into the box.
When Mbappé played up front with Radamel Falcao at Monaco, he favoured the left wing, coming in off the flank on to his right foot.
It would make sense to try this against Real. Put the 19-year-old where Neymar would have played, get him to test the pace of the defence and let Di María attack from the right.
Playing inverted forwards then gives more space for Dani Alves and Layvin Kurzawa to bomb forward from full-back and add to the attack.
Over his last six league games, whether he has started or not, Di María has contributed to the attack: on Saturday, he had eight shots on goal, completed three dribbles and managed one key pass; but, on average over that run of games, he has taken 3.16 shots, landing 1.5 on target; he has also completed 2.16 dribbles and 1.66 key passes.
Per 90 minutes, his expected goals is 0.56 this term, just behind Mbappé at 0.63, and his expected assists stands at 0.29. He is obviously nowhere near the level Neymar provides, but he can still be the hero.
Di María may not be what PSG are looking for in the future, they made that clear with their purchases this summer, but he is the weapon they have right now and is more than capable of taking the game to Zinedine Zidane’s men.
When the French side ripped Barcelona apart 4-0 last term, it was he, Draxler and Cavani who inflicted the damage. How Di María would love to step up to the plate once again, inspiring his club to an unforgettable victory against his former team.