Victorian union members knocked back the government's updated offer of a 28.3 per cent pay rise over the next four years on Tuesday.
Australian Education Union Victorian branch president Justin Mullaly told reporters educators were calling for a better offer to combat ongoing resourcing and staffing pressures.
"They've had a gutful," he said.
"The government's done precious little to do anything meaningful to address that and our members are carrying the weight of all the excessive workload."
There was a narrow majority of 51 per cent of members who opted to turn down the offer, compared to an almost 49 per cent who voted in favour.
"The critical thing is that the majority have decided to reject it," Mr Mullaly said.
Union educators have been locked in a pay dispute with the government for nearly a year, with graduate teachers - the worst paid in the country - earning $13,000 less than those in the Northern Territory, who are the best paid.
Members had been pushing for a 35 per cent pay rise over four years after rejecting an initial offer of an 18.5 per cent increase over three years.
Deputy Premier and Education Minister Ben Carroll described the outcome as disappointing, urging the union leadership to stop the strike.
"This deal would have made Victorian teachers and education support staff the best paid in the country together with the best conditions," he said.
"I urge the AEU leadership to call off the planned strike, because students should be in classrooms and parents shouldn't be left scrambling for childcare or losing a day's pay."
Thursday's strike is set to be reminiscent of scenes in March, where more than 35,000 teachers, principals and education support workers walked off the job for the first time in 13 years.
In June, teachers voted down a revised state government offer on pay and conditions, despite their union reaching an in-principle agreement with the government.
A fresh statewide strike was announced by teachers for Thursday, prompting the government to table another an eleventh-hour pay offer.
Teacher Liz Walsh, a member of Socialists in Schools, celebrated the move to reject the offer.
"We have suffered for so long, with wages falling behind inflation and workload levels at crisis points," she said.
"Thousands of people have quit in despair, but now is our chance to turn the situation around."
Unionised public school educators will gather in Melbourne's CBD on Thursday for a planned rally to coincide with the strike.
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