The Independent Education Union of Australia's NSW branch is filing an application with the Fair Work Commission on Friday to lift pay for staff at more than 100 community-based preschools in the state.
"We need a 25 per cent increase for beginning teachers and more for experienced teachers working in preschools," secretary Carol Matthews said.
Early career school teachers are making almost $15,000 more per year than their colleagues in preschools, while experienced teachers can earn almost $32,000 more per year, Ms Matthews said.
Lifting wages for teachers in the highly feminised preschool sector could also help narrow the gender pay gap, while assisting parents juggle carer responsibilities, she said.
No one becomes a teacher to get rich, Premier Chris Minns told reporters on Friday.
"They do it because they passionately believe in the work that they're doing," he said.
"The government would never take advantage of that, that goodwill, that sense of public service. What we need to do is sit down and work out a way of getting real wage growth over time to keep people in the sector."
Public servants have been offered 10.5 per cent pay rises over three years but multiple unions are seeking more.
However there are limits to what the state can provide, Mr Minns said, leaning on the state's recently re-established Industrial Court to protect from ongoing strikes or conflict.
"It's really a challenge ... to ensure we've got enough frontline workers that are educating the next generation," he said.
"If we can't come to an agreement with our essential workers, then we've got a mechanism to decide some of these disagreements."
Prue Car says access to affordable preschool is vital to ensure children get the best start in life. (Bianca De Marchi/AAP PHOTOS)
Access to affordable preschool is vital to ensuring children get the best start in life, Education and Early Learning Minister Prue Car said.
"Their transition to kindergarten is more seamless, it means the literacy and numeracy opportunities in primary school are able to be harnessed by children that have accessed quality preschool," she told reporters.
The government pumped more than $1.8 billion into early education in the June budget, providing fee relief and supporting the ongoing construction of 100 public preschools by 2027.
About 95 per cent of eligible children access preschool, Ms Car said, but the government needed to provide some help to get the remaining five per cent enrolled.
It remains up to parents whether and when they decide to send their children to preschool but subsidies are available for children from the age of three and Ms Car does not want cost-of-living pressures making the decision for them.
"Whether the fees are affordable or not will make a difference, whether you can send your child to preschool or not," she said.
"We don't want families to have to make that choice."
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