Primary school principals and teachers have voted to walk off the job in a series of rollings strikes.
The industrial action is set to be held in the week starting November 12, affecting thousands of families around the country.
It follows a national strike on August 15 and NZEI members' rejection of a second offer by the Ministry in late September.
NZEI Principals' lead negotiator Louise Green said the unprecedented level of industrial action by primary teachers and principals showed the severity of the crisis in our schools.
"We're at crisis point for recruiting and retaining teachers in this country. I've had principal colleagues in tears with the stress of trying to ensure a teacher in every classroom. Meanwhile the huge workload and lack of resources for children with additional learning needs is driving teachers out of the profession," she said.
Tonight's decision follows a 10-day electronic ballot.
The Ministry of Education said following the results of the ballot, the Ministry and union would urgently seek facilitated bargaining under the Employment Relations Act.
"This process will facilitate reaching settlements for primary principals and primary teachers."
In a statement, Education Minister Chris Hipkins said there was still a lot of water to go under the bridge before the proposed industrial action was due to take place.
"The Government is pleased the Ministry of Education and the NZEI are urgently seeking facilitation under the Employment Relations Act. This will advance the process to help reach settlements with primary principals and teachers."
National Party spokesperson for education Nikki Kaye said the second strike raises questions around the Government's collective bargaining for schools.
"Other groups in the public sector like the New Zealand Police have been offered more, and the Government created massive expectations for teachers during the election campaign that they are now failing to meet," she said.
"The Government has committed billions of dollars for tertiary students, has billions more cash in surplus so they should be able to give teachers a better offer.
"I believe there is huge public support for teachers getting more. National didn't have the same options that Labour has but now that New Zealand has larger surpluses we have options."
Teachers' lead negotiator for the union, Liam Rutherford, said teachers and principals did not want to inconvenience their students and school communities - or lose a day's pay.
"However, we all know what is at stake, and the importance of standing our ground on fixing the crisis in teacher recruitment and retention. Our students deserve better, and this Government can do better - their $5.5 billion surplus confirms it," he said.
Meanwhile, NZEI Te Riu Roa president Lynda Stuart said that while strikes would go ahead "we have agreed to continue to try to seek a resolution".
NZEI and the Secretary for Education had committed fully to seeking an agreed settlement before November, when the strikes are due to commence.
"Tomorrow, both parties will jointly refer the collective bargaining to the Employment Relations Authority for urgent facilitation."
Facilitation is a statutory process.
Stuart said earlier tonight the institute had had "some conversations" with the Ministry of Education since teachers voted "overwhelmingly" last month to reject the ministry's latest offer of a 9.3 per cent pay rise over three years.
Strikes have been planned in Auckland on Monday of that week, North Island provinces on the Tuesday, Christchurch on the Wednesday and South Island provinces on the Thursday, culminating in a march on Parliament during a strike in Wellington on the Friday.
Education Minister Chris Hipkins told secondary teachers this month that their claim of an immediate 15 per cent pay rise was "out of the ballpark".
But the Government is believed to be keen to avoid further strikes after almost all primary and intermediate schools were closed by a one-day strike on August 15.
NZEI have lodged claims for a 16 per cent pay rise over two years plus more staffing, including special needs coordinators in all schools and reducing the staff/student ratio in Years 4 to 8 from 1:29 to 1:25.
The Ministry of Education initially offered 6.1 per cent over three years to most teachers, but bigger increases of 14.2 per cent over three years for beginning teachers.
After the first strike it offered 9.3 per cent over three years across the board, in line with deals agreed with nurses and offered to police officers.
It has not yet offered anything on staffing, but Associate Education Minister Tracey Martin has published a draft plan to fund learning support coordinators in all schools. The plan did not include any costings and said the coordinator role "will require a funding decision before it can be confirmed".