The rail union says workers are "dismayed and furious" at the NSW government after it sought to block them from taking industrial action, saying it could harm the economy.
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Sydney Trains and NSW TrainLink have applied to the Fair Work Commission to suspend or terminate all industrial action on the state's rail network.
The protected industrial action by workers is planned to begin on Monday and could affect rail services in Sydney and regional NSW through to March 7.
It comes amid a long-running dispute over safety provisions and conditions between the government and the Rail, Tram and Bus Union.
"Rail workers are completely blown away by the NSW government's actions today," Alex Claassens, secretary of the RTBU, said Friday.
Mr Claassens accused the NSW government of "pure hypocrisy", saying it had "refused to meet with the rail unions for formal negotiations since 3 February".
This comes after Transport for NSW secretary Rob Sharp said he and his executives met with unions this week, and held more than 30 meetings with the unions over the past six months.
"The people of NSW would be appalled if they knew what the government is trying to do to their public transport network, selling it off piece by piece and not prioritising safety concerns raised by workers, just so they can save a buck," Mr Claassens said.
He said Transport NSW still needed to address a "laundry list of safety and employment issues" raised by employees.
The industrial action could disrupt commuters and "cause economic harm to the NSW economy", a statement from the NSW government said on Friday.
Mr Sharp said the action was taking place at the same time NSW Premier Dominic Perrottet had announced an easing of restrictions across the state.
"Our number one focus is to ensure the travelling public can get where they are going safely and can rely on the public transport system at this critical time," he said.
"During our negotiations, we have made reasonable concessions and we continue to encourage the unions to come back to the bargaining table rather than take action, to work with us to make two new Enterprise Agreements that benefit not just our employees, but also our customers."
Australian Associated Press
