The Scottish Secondary Teachers’ Association (SSTA) said 80% of its members rejected the deal put forward by local authority body Cosla.
The negotiations come in the midst of a cost-of-living crisis caused by rising inflation and increasing energy prices, with Cosla locked in industrial disputes with education staff and cleansing workers in recent months.
Seamus Searson, general secretary of the union, said: “SSTA members have given everything in the last number of years to keep education going and to ensure that all young people did not lose out during these difficult times.
“Teachers are walking away from the job because of the excessive workload and a poor pay offer only adds insult to injury.”
He urged the Scottish Government to step in and help resolve the situation.
The dispute between council staff and Cosla was resolved last month after the intervention of First Minister Nicola Sturgeon, with unions praising her role in bringing negotiations to an end.
“The Scottish Government must step up to the plate and be prepared to put in place a pay offer that will retain teachers and recognise their tremendous efforts over the last few years,” Mr Searson said.
“Teachers are already struggling to keep schools running with morale very low and Cosla’s disparaging pay offer only adds to their feeling of being grossly undervalued.”
A spokesman for the Scottish Government said: “We are committed to supporting a fair pay offer for teachers through the Scottish Negotiating Committee for Teachers, the body that negotiates teachers’ pay and conditions of service.
“Industrial action would not be in anyone’s interest, least of all learners and parents.”
Meanwhile, workers at the Scottish Qualifications Authority (SQA) have suspended a strike following a new pay offer.
The SQA said the offer would mean an overall average increase of 5.9 per cent. Industrial action had been announced for 15 and 16 September.