Siobhian Brown, MSP for Ayr, said she believed the empty houses could be used to house families in South Ayrshire and that the area was ready to accept and welcome Afghan families.
The homes, which are mostly situated around Prestwick Airport, have been left empty ever since the helicopter search and rescue operation HMS Gannet was decommissioned in 2016.
Earlier this year it was revealed nearly 11,000 MoD homes were empty across the UK, with 900 unused in Scotland.
Ms Brown said: “The UK Government should be maximising every opportunity it can to find a home for Afghan refugees fleeing a horrific situation. In South Ayrshire, we currently have around 100 homes that are still owned by the MoD, but no one has lived in them for at least five years.
“This is an opportunity for the UK Government to show its compassion for refugees coming from Afghanistan that they are able to provide them a safe and warm home where they can start to rebuild their lives."
She added: “The UK Government must take its share of the responsibility for creating this situation and using disused MoD homes will provide them with an option for a number of families who have had their lives turned upside down.
“Boris Johnson should commit to increasing the number of refugees that the UK brings in and maximising unused sites like the one at Prestwick Airport will allow the UK to take in more refugees and take responsibility for the situation.”
A report by the Public Accounts committee two years ago described the MoD’s failure to reduce its empty housing stock as “scandalous” at a time of national housing shortages.
The number of empty military homes in Scotland in 2020, which have their upkeep or rent paid for by the taxpayer, was down from 1,087 in 2019 and 1,129 the year before.
In 1996, the Ministry of Defence sold off most of its service family estate to Annington Property Limited and agreed to rent it back for up to 200 years.
A spokeswoman for the MoD said that 100 units of service family accommodation had already been offered to local authorities to lease to house Afghan evacuees.
She said the ministry was considering whether further properties could be made available.
The spokeswoman said: “Work is underway across the whole of government to ensure that those Afghan nationals who stood side by side with us in conflict, their families, and those at highest risk who have been evacuated, are supported as they now rebuild their lives in the UK.
“We continue to work closely with the Ministry for Housing, Communities, and Local Government, the Home Office, and devolved administrations to identify how we can best assist, to ensure that these families are housed in areas in which they can easily access services they need.”