Leclerc, the points leader and two-time race winner so far in 2022, made the most of the extreme track evolution on the brand new street track to set the benchmark at 1m31.098s.
That gave him a slender cushion of seven hundredths of a second over Russell, as the W13 sports a more efficient front wing plus lower downforce specification rear and beam wings for this weekend.
Max Verstappen led his Red Bull stablemate Sergio Perez inside the top four, but the reigning champion was hobbled by the high Florida temperatures that truncated his running.
Nicholas Latifi led the Aston Martins of Lance Stroll and Sebastian Vettel out of the pits to a chorus of cheers as the capacity 80,000 crowd clapped eyes on the cars for the first time.
All but Mick Schumacher took to the 3.3-mile circuit within the first two minutes of the hour-long session, the majority completing their early laps on the medium C3 tyre.
Zhou Guanyu and Perez both ran deep into Turn 1 as they pushed the limits of the sweltering asphalt, which was recorded at more than 50 degrees Celsius.
Meanwhile, Russell was forced to jump on the brakes and stop in the pitlane to avoid the Alpine of Fernando Alonso as the two-time champion emerged out of the garage.
To get acclimatised to the new venue, most teams did away with the customary installation laps and kept their drivers on track – Schumacher joining eventually after eight minutes.
The green track surface proved particularly slippery as Yuki Tsunoda and Leclerc had to rejoin after both lost the rear and spun their cars, while Verstappen pushed the limits by tapping the outside wall at the Turn 16 left-hander.
Despite their early scares, Leclerc ran to the top of the times with his 1m34.846s to hold a three-tenth advantage before Verstappen bolted to a 1m33.44s to run clear by 0.7s.
Ferrari and Red Bull continued to swap places at the top of the timing board as the track evolved to offer up more grip, bringing the lap times under the 1m33s barrier.
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