Sir Keir Starmer has called on the government to "use the window" of the February half-term to vaccinate all teachers and support staff.
Speaking at Prime Ministers Questions, the Labour leader said reopening schools must be a national priority.
Labour wants to bring forward the vaccination of key workers alongside others in high risk groups.
But Boris Johnson said the proposal would "delay our ability to move forward out of lockdown".
The PM said teachers in the top nine priority groups would be vaccinated as a "matter of priority", adding: "I know how deeply frustrating it is, the extra burden that we have placed on families by closing the schools."
Mr Johnson said he remained confident that the top four priority groups - taking in all over-70s, health and care staff and elderly care home residents - would receive a first jab by mid-February "if we can get the supply" of vaccines.
By the end of April those in the next five priority groups, including all over-50s and younger adults with underlying health conditions, should have been offered a jab, under the government's plans.
Labour wants to see workers in critical professions - such as police officers, firefighters and transport workers, as well as teachers - vaccinated alongside these groups.
'Safe to reopen'
Shadow health secretary Jonathan Ashworth said: "The NHS rightly deserve congratulations for their impressive and speedy roll out of vaccinations.
"But now we need to go further and faster.
"Not only will vaccination acceleration save lives it will help us to carefully and responsibly reopen our economy and crucially ensure children are back in school as transmission reduces."
But asked about the proposal in the Commons, Mr Johnson said it would "take vaccines away from the more vulnerable groups and... delay our ability to move forward out of lockdown".
The government has said it will prioritise the reopening of schools as it begins the process of lifting lockdown restrictions, but in a Commons statement after PMQs, Mr Johnson indicated that schools would remain closed until early March.
"We hope it will... be safe to begin the reopening of schools from Monday, 8 March, with other economic and social restrictions being removed thereafter as and when the data permits," he told MPs.