Team Global Express unveiled 43 battery-powered trucks on Thursday, in addition to significant renewable energy and charging infrastructure at its western Sydney depot that will test the technology over the next five years.
Prime Minister Anthony Albanese called the trial a "game-changer" that could help other companies work out ways to drive down vehicle emissions and costs.
The delivery comes more than a year after the company teamed with the Australian Renewable Energy Agency to announce the trial that is expected to see 60 electric trucks stationed at its Bungarribee depot.
The 43 electric trucks, including Volvo eFL and Daimler Fuso eCanter vehicles, will be used to deliver parcels around Sydney and, when the full fleet is delivered, will replace one third of the company's fleet.
The heavy vehicles will be recharged using equipment supplied by Jet Charge, and a one-megawatt battery storage system powered from 400 kilowatts of on-site solar panels.
Mr Albanese, who attended the vehicle launch, said the electric truck trial would show businesses how to reduce fuel costs while making significant emission cuts.
"This is a game-changer," he said.
"We know that around about over 20 per cent of Australia's emissions are due to the transport sector and one in four of those emissions is due to buses and heavy vehicles."
The renewable energy agency will provide $20.1 million to fund the five-year trial from the federal government's Driving the Nation program while the logistics firm contributes $24.1 million.
Team Global Express group chief executive Christine Holgate said deploying electric trucks in such large numbers would prove to be an invaluable test for the wider transport industry.
"As part of our partnership with ARENA, we will be sharing the knowledge we gain from the trial with other industry providers to benefit the entire sector," she said.
"We are thrilled that these trucks are on Sydney roads, delivering parcels directly to residential and commercial customers."
The trial will eventually include 24 Daimler electric vehicles and 36 Volvo trucks - the company's largest order of medium-duty electric trucks worldwide.
Volvo Trucks president Roger Alm told AAP its partnership with the logistics firm was important to prove the value and practicality of heavy-duty electric vehicles.
"We have big hopes that Australia will really take off in terms of electrification," he said.
Mr Alm said the company, which has announced plans to build electric trucks at its Brisbane factory from 2027, intended to replace all its diesel trucks in operation by 2050.
The electric truck trial also comes just days after the Queensland government announced changes to allow heavy-duty electric trucks on selected roads, making the state the fourth jurisdiction to allow the vehicles.
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