Staff at Goodstart Early Learning voted for a new enterprise agreement that would trigger a 10 per cent pay increase from December, followed by a five per cent rise 12 months later.
The more than 16,000 educators at the organisation will be among the first in Australia to have the government's pay rise for the sector come into effect.
Parliament passed laws earlier in November for the 15 per cent rise over two years, which is set to increase the award rate by $155 a week by the end of 2025.
The $3.6 billion proposal, due to flow on to 200,000 workers, was put forward as a way to address staff shortfalls in the sector.
Childcare centres could only have the wage rise for its staff if it agreed to cap fees for parents to 4.4 per cent over 12 months.
 The wage rise for early childhood educators was long overdue, ACTU assistant secretary Joseph Miller said.
"Early childhood educators have been taken for granted for too long and this pay boost comes off the back of years of campaigning that has proven beyond any doubt the quality, skill, and value of their work," he said.
"For many who have struggled to meet the cost of daily essentials, it will give them more stability in their lives."
As part of the enterprise agreement with Goodstart, a multi-employer agreement between 64 employers in the sector and the United Workers Union means the wage rises extend to a further 12,000 employees in the sector.
The increases would ensure staff stay in the industry for longer, United Workers Union director of early education Carolyn Smith said.
"These agreements are a game changer for early childhood education and care providers across Australia," she said.
"This pay rise has been the missing piece in providing children and families the high-quality early education and care they need."
The government is also examining a possible move to universal childcare, after the Productivity Commission recommended it be made free for low-income families.
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