The Army is to start helping with the vaccination programme in NHS Lothian and NHS Lanarkshire.
More than 60 personnel will be deployed in Scotland as part of Operation Rescript for up to five weeks.
NHS Lothian said the army would have capacity to deliver up to 3,600 vaccines per day in its area.
NHS Lanarkshire said it planned to offer 1,000 extra second doses a day for a week as a result of the army’s assistance.
The army deployment is part of the UK government’s response to “variants of concern” spreading throughout the country.
Dr Mark Russell, who is leading the Covid vaccination programme in Lanarkshire, said the extra available appointments are for anyone needing a second dose who received their first dose before 1 April.
He said: “We have been able to increase the number of second dose appointments we can offer due to the support we are receiving from the Armed Forces.
“This means we can give people the opportunity to bring forward their second doses if they wish, which will help to protect more people as quickly as possible.”
The extra slots are also available for those who want to bring forward an existing second dose appointment.
The army will be assisting in the NHS Lothian area from Wednesday.
The Army is also being deployed to assist the vaccine roll-out in north-west England.
Armed forces personnel will provide “ongoing assistance” with administering vaccines, logistics, planning support and carrying out “surge testing” where needed.
In Scotland, 63 personnel will be split across NHS Lothian and NHS Lanarkshire with vaccinators, health professionals and command-and-control managers providing support.
UK Defence Secretary Ben Wallace, said: “The armed forces continue to show their incredible versatility and flexibility, deploying wherever and whenever they are needed in support of this national vaccination effort.
“I am delighted to see that across all corners of the UK, military personnel are working side by side with their NHS counterparts to help get the British public vaccinated as quickly as possible.”
More than 3.3 million people aged 18 or over in Scotland have so far received a first dose of a Covid vaccine, with about 2.2 million now fully vaccinated.
Public health officials have said they want to accelerate the vaccine programme to help protect against the Delta variant which is spreading rapidly in the UK.
The Scientific Advisory Group for Emergencies has said it is highly likely the variant, which was first seen India, is more transmissible than the Kent variant and that it is a “realistic possibility that it is as much as 50% more transmissible” , according to the BBC’s health and science correspondent.
Scotland’s national clinical director, Prof Jason Leitch, said pushing the vaccine roll-out in Scotland and across the globe was vital in guarding against new variants.
“So far the vaccine – particularly two doses of the vaccine – are successful for the variants we have, but eventually one will probably get away from us and we’ll have to adjust the vaccines over time,” he told BBC Scotland.
“What we’re trying to do is win the race now, get the incidence down around the world, not just in Scotland, and then the vaccine scientists can work on a new vaccine for us as they monitor the virus around the world.”
On average, about 48,000 people a day in Scotland are currently receiving their first or second dose of a Covid vaccine.
UK Health and Social Care Secretary Matt Hancock said: “We have vaccinated over three-quarters of UK adults with a first dose and half of adults with a second dose.
“That is a huge effort across the healthcare system and beyond – and I am incredibly grateful for the amazing role our armed forces have played in this.
“We know how effective the vaccine is, thousands of lives have been saved and thousands of hospitalisations prevented.”
As part of the UK government’s response to variants of concern, 400 trained vaccinators from across the armed forces are available to be deploy when needed, with 4,300 service personnel at “high readiness”.
The Army has already been used in Scotland, helping establish 80 new Covid vaccine centres across the country in January .
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