NSW Premier Chris Minns will wade into an escalating pay dispute with his state's 50,000 nurses and midwives after rebuffing earlier demands to address striking workers.

At least 5000 nurses and midwives took to the streets on Tuesday over a rebuked demand for an immediate 15-per-cent pay increase.

Posters at the rally called the premier a liar, accused him of making hollow promises and compared him to a catheter for "taking the piss".

It marked the largest rally against the Labor government since coming to power in March 2023.

Thursday's meeting with union leadership would cover "everything" to do with wages and conditions including the log of claim prior to the election and after the election, the premier said.

The sit down had been organised for a long time, he said.

"The fundamental disagreement ... is that in one year they want us to make up the wage suppression imposed on them by the Liberal party," he told parliament on Wednesday.

"The government does not have the budget to do that in one year."

The NSW Nurses and Midwives Association says its one-off pay increase would address a gender pay gap in hospitals and could be covered from improving patient data entry to collect more federal funding.

Opposition health spokeswoman Kellie Sloane expressed scepticism about the meeting being long organised.

"This is an eleventh hour move from a premier who has been absent from the negotiating table and is presiding over industrial chaos in this state," she told AAP.

"Chris Minns didn't front up to nurses yesterday, because he doesn't want to admit publicly that he gave them false hope and has failed to deliver."

Mr Minns on Wednesday rejected accusations that he had betrayed nurses as some rally posters alleged.

Improved nurse-to-patient, a new independent industrial register and the removal of the coalition's cap on wage rises - all calls from the nurses union - had been implemented by his government, he said.

Rectifying the pay gap could happen over a number of years, he said.