Audi Sport Abt Schaeffler's Lucas di Grassi led the way in a red-flagged practice one ahead of the Santiago E-Prix, edging Mahindra Racing's Pascal Wehrlein.
Di Grassi, who won the Drivers' Championship in Season Three of the all-electric single seater series, set a best time of a 1m 08.630s to top the timesheets, with Wehrlein, who made his Formula E debut at the Marrakesh E-Prix earlier this month, 0.146s adrift of the Brazilian racer.
Sam Bird, who secured pole position in Marrakesh, fronted a 3-4 in practice for Envision Virgin Racing, 0.358s off di Grassi's session-topping pace while Robin Frijns was a further 0.071s adrift of this team-mate.
Reigning Formula E champion Jean-Eric Vergne completed the top five for DS Techeetah while Antonio Felix da Costa was sixth fastest for BMW i Andretti Motorsport, 0.845s off the pace.
Oliver Turvey posted the seventh fastest time of the session for NIO, 0.012s adrift of da Costa while Andre Lotterer was eighth in the second DS Techeetah, heading Daniel Abt who was ninth fastest in the second works Audi. Jerome d'Ambrosio completed the top 10.
Panasonic Jaguar Racing's Mitch Evans was 11th fastest, 0.967s slower than di Grassi while Alexander Sims followed in 12th for BMW.
Edoardo Mortara fronted a Venturi 13-14 result for Venturi as the Monegasque squad's difficult season continues while Gary Paffett completed the top 15 as the lead HWA driver, using Venturi's VFE05 powertrain.
Nelson Piquet Jr was 16th in the second Jaguar and was followed by Jose Maria Lopez, Oliver Rowland, Stoffel Vandoorne and Maximilian Gunther who experienced three power shutdowns in the early stages of practice after failing to complete any running during Friday's shakedown session.
Tom Dillmann was 21st while Sebastien Buemi rounded out the field as the slowest runner after crashing his Nissan e.dams IM01 13 minutes into the session, clattering the inside wall of Turn 6 after locking both of his front tyres.
With extensive damage to the right-hand side of the car, Nissan faces a large repair job ahead of FP2, with it being likely that the Swiss racer will miss second practice at the Parque O'Higgins Circuit.
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