The Frenchman, who moves to LCR Honda for 2024, set a 1m30.191s at the end of 45-minutes of running to lead the opening practice session of the season finale at Circuit Ricardo Tormo.
Gresini rider Di Giannantonio finished second, 0.187s off the quickest time, having led for much of the session to continue his recent strong form.
Title rivals Jorge Martin (Pramac) and factory Ducati rider and reigning champion Francesco Bagnaia finished the session third and 13th respectively. Bagnaia must outscore Martin by four points in the sprint race to clinch his second consecutive title for the Italian manufacturer before Sunday’s grand prix.
Gresini’s Alex Marquez set an early benchmark to lead with a 1m34.555s, but was quickly bettered by Zarco with a 1m33.064s.
Fellow Ducati rider Marco Bezzecchi (VR46) and Martin then went faster, with Martin leading 0.006s ahead.
There were two crashes in quick succession 10 minutes into the session, with Honda rider Joan Mir crashing at Turn 8 for his 24th fall of the season, before Alex Marquez went down at Turn 1 after losing his front end in the chilly conditions.
Mir went to the medical centre following his incident and was yet to emerge by the end of the session.
Di Giannantonio then went top for the first time, setting a 1m30.851s ahead of Martin. The Italian currently has no ride for next year, but is widely expected to replace Luca Marini at VR46.
Photo by: Gold and Goose / Motorsport Images
Francesco Bagnaia, Ducati Team
He continued to lead at the halfway mark, while Bagnaia was 1.9s off the pace in 21st – not an unusual position for the factory Ducati rider on a Friday morning.
Marc Marquez was next to take the top spot on the timesheet with a 1m30.564s, hoping for a fairytale farewell as he heads into his final weekend with Honda after 11 years, though he admitted on Thursday that he “cannot try any crazy things” in Valencia.
Factory Aprilia rider Maverick Vinales then bettered his time by 0.03s, as further back Bagnaia improved to ninth.
Heading into the final 10 minutes, Di Giannantonio reclaimed the top spot with a 1m30.378s, 0.145s quicker than Bezzecchi.
LCR’s Takaaki Nakagami was the third faller of the session as he crashed at Turn 8 in an almost identical incident to that of fellow Honda rider Mir, prompting a brief yellow flag.
Zarco’s quickest time came in his final lap of the session to lead from Di Giannantonio and Martin. Bezzecchi was fourth, with…
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