Beckham was on Tuesday named in coach Carlo Ancelotti's 20-man squad, which is without suspended duo Zlatan Ibrahimovic and Marco Verratti.
With winger Jeremy Menez also sidelined by injured Beckham, who came on for Verratti in the weekend's shock 1-0 loss at Reims, could feature.
The 37-year-old has not played in Europe's premier club competition since AC Milan went out to his former club Manchester United at this same stage three years ago.
Beckham watched on from the stands in the opening leg at the Mestalla, when PSG claimed their 2-1 advantage and top-scorer Ibrahimovic needlessly saw red in the final moments.
The Swede's absence, plus the weekend's surprise loss, has ensured PSG will remain on high alert at the Parc des Princes on Wednesday night.
And Ancelotti admitted Beckham - who has made a single start since his deadline-day move - could have a significant role to play if PSG are to reach the last-eight for the first time in 18 years.
"Of course we need him (Beckham) as at the same time we need the quality and ability of the other players in this game," Ancelotti told a press conference.
"He has played two games (in the past week). The first game 85 minutes the other game 25. He played well with no problem.
"He has arrived at this team with his quality and his character - everything is Okay."
Valencia's French defender Aly Cissokho has warned that Valencia will arrive in Paris believing they can overcome their deficit and go through.
"In football nothing is impossible," he told a press conference in Valencia. "We may have lost at home but we still have our chance.
"From our point of view we will have to be very sturdy defensively and then score the opportunities that come our way.
"We have to play our game but most of all we can not concede a goal."
Valencia striker Nelson Valdez underlined the importance of the game for the Spanish club, not just on the field, but also off it.
While PSG have become one of the richest clubs in Europe following the arrival of their new Qatar-based owners, Valencia are currently cash-strapped.
"We know how important this is for the club, to continue participating in European competition," Valdez told www.uefa.com.
"I think the PSG match will be crucial for us to discover what level we are at. There are only strong teams left in the Champions League now, so we have to show we belong here."
Valencia welcome back Ever Banega and Cissokho after they were suspended for the weekend's 2-2 derby draw with Levante.