Real offloaded the Argentine to Manchester United in part to fund president Florentino Perez's policy of cherry-picking the standout performers at the World Cup, with Germany's Toni Kroos and James Rodriguez of Colombia arriving shortly before Di Maria's move to England.
Following a failed season at United the 27-year-old Di Maria, who is nicknamed 'Fideo' (Noodle) due to his wiry frame, moved to the French capital in search of a new lease of life and has made a solid, if unspectacular, start to his Ligue 1 career.
He was a key figure for Real during his four years in Madrid and was named man of the match when they beat city rivals Atletico 4-1 to clinch the 'Decima', a record-extending 10th European Cup crown, in his final season.
Di Maria's electric run helped set up Gareth Bale to put Real 2-1 ahead. He will also be remembered for the superb cross he sent over for Cristiano Ronaldo to head home and win the 2011 King's Cup final against Barcelona.
"If I score against Madrid I will not celebrate because at the bottom of my heart I have not forgotten what I experienced there with the Decima," Di Maria told French TV.
A depleted Real strolled to a 3-0 La Liga win at home to Levante on Saturday.
Coach Rafa Benitez is hoping some of the players who were missing through injury, including captain Sergio Ramos, midfielder Luka Modric and forward Karim Benzema, will be back for the clash at the Parc des Princes.
Forward Bale looks certain to miss the game after tests on Monday showed he has a calf injury.
PSG have been boosted by Zlatan Ibrahimovic's recent performances that suggest he is close to top form after injury disrupted his start to the season.
The Sweden striker has netted six goals in his last four Ligue 1 outings and PSG geared up for Wednesday with a clinical 2-0 win at Bastia on Saturday thanks to an Ibrahimovic double.
Coach Laurent Blanc rested his regular midfielders, with Thiago Motta coming off the bench on the hour and Di Maria, Marco Verratti and Blaise Matuidi not even in the squad.
PSG and Real have a maximum six points from two matches in Group A.
(Writing by Iain Rogers, editing by Tony Jimenez)
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