The Federal Government will compensate regional NSW for Pfizer doses that have been redirected to Sydney.
Prime Minister Scott Morrison said 185,000 doses would be sent to NSW over the next two weeks in an effort to raise vaccination rates.
The extra doses will arrive on August 9 and 16.
"We are ensuring that the doses that were reallocated from Newcastle and the Hunter by the state government are replaced in full," Mr Morrison said.
About 40,000 Pfizer doses have been taken out of regional NSW for Year 12 students.
"This is another shot in the arm for the state's vaccination rollout," Mr Morrison said.
"Every vaccination can save a life."
Parliamentary Secretary for the Hunter Taylor Martin, a NSW upper house member, welcomed the announcement.
"I'm grateful that the Prime Minister has heard the call from across the Hunter and Central Coast to have the doses replenished that were reallocated last week to HSC students," Mr Martin said.
"I really want to thank those people - whose vaccination was deferred this week - for their enthusiasm to get vaccinated.
"Hunter New England Health will be in touch with people to rebook their appointments."
Maitland Christian School employee James Thomson, who is also the Nationals candidate for the federal seat of Hunter, said he was on his way to get a COVID test after two students at the school tested positive.
"I think the federal government has taken a common-sense approach by replacing the Hunter's Pfizer vaccines. We should never have been put in this situation in the first place," he said.