The Rail, Tram and Bus Union will deactivate Opal readers and gates from next Wednesday, indefinitely, until a resolution is reached, NSW secretary Alex Claassens said.
The strategy is designed to turn up the heat on government and senior bureaucrats.
"They are the ones responsible for this mess, they can now live with it," Mr Claassens said on Wednesday.
Premier Dominic Perrottet said the union was turning off the machines because 90 per cent of passengers were still tapping on when the gates were left open last month.
"That shows the people of NSW just want to get on with it. That's what I expect of the union," he said.
Not all stations have gates, but Opal poles at suburban platforms will also be deactivated.
"You can tap all you like but nothing's going to happen," Mr Claassens said.
The deactivation will be coupled with a ban on issuing fines.
The union believes it's within its rights but Transport for NSW will try and stop it proceeding.
"Sydney Trains does not consider this ban to be protected or lawful action and is seeking legal advice, and will write to the RTBU seeking a withdrawal of this action," a spokesman said in a statement on Wednesday.
Opposition Leader Chris Minns called for negotiations to resume.
"I'm happy that industrial action at least is not inconveniencing the public, but no one wants industrial action," he said.
"We want an agreement between the two sides."
Also from September 21 there will be bans on wearing lanyards or name badges, station announcements on Opal issues and online training.
Mr Perrottet threatened to terminate the existing enterprise agreement at the end of August after a month of industrial action caused widespread disruption across several days.
He declared negotiations for a new agreement over and a final offer had been presented, but the unions rejected it and applied to the commission to continue bargaining.
The dispute returned to the Fair Work Commission on Wednesday, following a hearing on Friday and attempted conciliation.
Mr Claassens called the attempts a stalling tactic by the government.
"There is no point in coming to the conciliation table unless you've got the decision makers at the table," he said.
"We've been negotiating with (chief executives) … they've had to go through all these hurdles to get approval."
Ingmar Taylor SC, on behalf of unions, argued on Wednesday the government breached good faith bargaining by terminating negotiations and not identifying decision makers throughout.
NSW TrainLink transformation director Jasmin Streimer, the lead negotiator for the agency in bargaining since May 2021, told the hearing chief operating officer Dale Merrick was the decision maker.
"It's not a purely lateral hierarchy," she said.
Government ministers, the cabinet expenditure review committee they're part of and the department secretaries they can instruct were all involved in making decisions too, even if they did not attend bargaining meetings.
Ms Streimer accepted the offer presented to the union as "final" was incomplete, did not bind the government to provide the payments it promised, and the rail entities had still not provided a final version.
The union is seeking a 3.5 per cent annual wage rise - above the three per cent NSW government cap it argues does not apply to them - with an additional cost of living supplement based on a Queensland government model.
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