Defending series champion Jean-Eric Vergne set the pace in a specially adapted session for DS Techeetah with a 1m17.342s.
The session was extended to 17:15 local time in Valencia due to the demonstration race overrunning after a lengthy stoppage.
Andre Lotterer was second fastest in the other DS Techeetah ahead of Sebastien Buemi’s Nissan once he had been allowed back into the session after going on track in his normal car.
He had driven the #22 car in the demonstration race earlier today.
Antonio Felix da Costa and Alex Sims rounded out the top five for BMW I Andretti Motorsport in what was a relatively disappointing session for the German manufacturer.
Sixth and seventh fastest were the Audi Sport Abt Schaeffler entries of Daniel Abt and Lucas di Grassi with Venturi’s Felipe Massa showing well in eighth.
Rounding out the top ten was Sam Bird in the Virgin Racing run Audi and Mitch Evans in the fastest of the Jaguars.
Eleventh place was Dragon Racing’s Jose Maria Lopez with Tom Dillmann in the fastest of the NIO’s and following them was Robin Frijns in the second Virgin Racing entry.
Nelson Piquet was fourteenth for Jaguar ahead of Oliver Turvey in the other NIO and Dragon Racing’s Max Gunther.
Rounding out the drivers who set lap times during the session were the Mahindra Racing duo of Jerome d’Ambrosio and Pascal Wherlein.
Venturi’s Edo Mortara and the HWA duo of Garry Paffett and Stoffel Vandoorne all didn’t set a lap time.
In the earlier session this afternoon, Sebastien Buemi was fastest for Nissan with a 1m17.773s, a lap time that was almost 3 seconds a lap faster than the DS Techeetahs of Jean-Eric Vergne and Andre Lotterer.
Fourth fastest was Mitch Evans for Jaguar ahead of the Venturis of Edo Mortara and Felipe Massa and the NIOs of Tom Dillmann and Oliver Turvey.
The Dragon Racing pairing of Max Gunther and Jose Maria Lopez were the only other drivers to set a lap time.
The drivers who didn't set a time were Sam Bird, Nelson Piquet, Robin Frijns, Stoffel Vandoorne, Lucas di Grassi, Garry Paffett, Alex Sims, Antonio Felix da Costa, Jerome d'Ambrosio, Daniel Abt and Pascal Wehrlein.