Combined with the hydropower used at its Jonquiere facility, the company said the smelter will generate one seventh of the greenhouse gases per tonne of aluminium when compared to the industry average.
Aluminium from the smelter is used in transportation, construction, electrical and consumer goods.
Rio Tinto Chief Executive Jakob Stausholm said this was its "most significant investment in our aluminium business for more than a decade."
"This investment is aligned with our strategy to decarbonise our value chains and grow in materials essential for the energy transition," he said in a statement.
Quebec is contributing Can$150 million (US$113 million) for the smelter upgrades.
Last October, the federal government also provided Can$222 million (US$165 million) to help a Rio Tinto subsidiary increase its production of critical minerals, including lithium, titanium and scandium.
The smelter expansion, the company said, will increase capacity by approximately 160,000 metric tonnes of primary aluminium per year, enough for 400,000 electric cars.
It will also add 100 permanent new positions at the completed facility.
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