A new rail line will run from Parramatta to Sydney's CBD, with stops at Sydney Olympic Park and the Bays Precinct, to ease pressure on the city's western line.
The project will be largely underground and is expected to be up and running in about a decade.
It will have a capacity of 40,000 passengers an hour in each direction.
"A metro line in western Sydney will effectively double rail capacity between Parramatta and the Sydney CBD, transforming the way we get around our city forever," Premier Mike Baird said in a statement on Monday.
The government said it would determine the number and location of stations along the route "through consultation with industry and the community".
Speaking at a press conference at Sydney Olympic Park on Monday, Mr Baird said it was hoped construction on the new line would begin within five years.
"We're not in a position where we want to determine either the final cost or final timeline, but it is underway," he told reporters.
NSW Transport Minister Andrew Constance said the rail link would not replace the previously flagged light rail line for Sydney's west.
"These are two very different transport projects with two very separate objectives," he said.
"Light rail is about connecting precincts.
"This project is obviously a mass transit solution which is going to lead to connectivity between Parramatta and the CBD and of course at the same time alleviate existing congestion pressure on the T1 line."
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