Chief Constable Iain Livingstone said hundreds of police officers and staff already have benefits from being given "surplus" vaccines - unused jabs which would otherwise have gone to waste.
He said he would continue to make the case to the Scottish Government that Police Scotland officers and staff should be a priority group, once the initial rollout of the vaccine to those aged 50 and above and those with underlying medical conditions has been completed.
The Chief Constable spoke as he gave his latest update to the Scottish Police Authority (SPA).
He stressed it was an "an absolute priority" for him to ensure the safety of his staff, saying this "goes to the core purpose of my duties as Chief Constable".
A paper from him ahead of the SPA meeting disclosed that by February 15, more than 400 officers and staff had received the first dose of the vaccination as part of an initiative in which local health boards give "surplus vaccines, which would otherwise be wasted, to frontline officers and staff".
Mr Livingstone said he was "pleased to report, to ensure where surplus vaccines become available which would otherwise be wasted, that they can be taken up by officers and staff working right across Scotland in local communities".
He added: "This is a real positive initiative which has provided already hundreds of officers and staff with vaccinations which otherwise would have been wasted."
The Chief Constable and other senior figures from Police Scotland will also "continue to discuss the national vaccination programme with the Scottish Government ministers and senior officials", he said.
The police will stress the "legitimate concerns of officers and staff about exposure they encounter during their daily duties".
He spoke about how the job of the police involved officers "taking themselves into situations of danger, taking themselves into places where people are breaching the coronavirus guidelines, and the anxiety and concern that comes from that".
He said: "There is, in my view, a strong case to protect officers and staff through vaccination, and through vaccination of officers and staff, therefore, protect the public that they serve.
"I will continue to advocate on their behalf into senior levels of government."
Mr Livingstone added there was a "very powerful case for police officers and police staff, indeed school teachers and nursery care workers and others involved in public life, key workers", to be a priority for vaccines.
The jabs are currently being given out in line with guidance from the Joint Committee on Vaccination and Immunisation, with Mr Livingstone saying this list was "clinically led" and focused on achieving the "greatest impact of vaccination".
But he told the SPA: "I think there is an understanding within government of the concerns of policing and I will continue to advocate on behalf of policing and voice those concerns in a proportionate and legitimate manner."