Describing the opening as a "starting point", Coregas executive general manager Alan Watkins said within a short period of time up to 10 trucks a day could be refilling at the station.
"The first company Remondis, a waste management company, will be running its first garbage truck on hydrogen," Mr Watkins said.
"Coregas is also expecting two heavy-duty prime movers from Hyzon motors to move gas from Port Kembla to customers."
He said a typical 400-kilowatt vehicle would be able to refuel in 15 minutes from empty at the station and travel 650 kilometres on a tank of hydrogen.
The $2 million hydrogen refuelling station has been built alongside Coregas' existing hydrogen production plant and transport hub for bulk hydrogen, within the Bluescope Steel terminal at Port Kembla.
From grey to green hydrogen
Mr Watkins said hydrogen was the only gas fuel that did not produce carbon dioxide when burnt.
"The fuel cell vehicles that we have seen today are producing steam, they have zero footprint," he said.
He said the refuelling time and payload were also advantages.
"There is no charge time in the same way an EV vehicle works and the payload is quite light," he said.
"The equivalent truck to the Hyzon vehicle here today would have to lose about six or seven tonnes of payload in battery weight — and that is important if you are going to run a commercial fleet and run long distances."
Coregas expects to convert its fleet of a dozen vehicles to hydrogen within the next couple of years.
At present, the station uses "grey" hydrogen created using natural gas.
But the company aims to transition to "green" hydrogen, from less polluting, carbon-neutral sources.
"We have a kind of obsession with the colour of hydrogen at the moment," Mr Watkin said.
He said the company was in advanced negotiations to convert to biogas, which he said would create carbon-neutral green hydrogen.
Building the transition workforce
State Minister for the Illawarra and Keira MP Ryan Park was the first to refuel a truck at the station's launch today.
"This is going to be a part of the mix as we start the process of reform in the way we provide fuel and energy to our prime movers and heavy vehicles," Mr Park said.
The state government is set to introduce a fleet of 8,000 hydrogen buses, with trials running on the Central Coast already.
Wollongong MP Paul Scully said he hoped to see the bus trial extended to the Illawarra.
He said the state government was working with TAFE NSW to help build the work force required for the transition.