Jeane Freeman said vaccinators will help immunise the population during evenings and weekends.
It came as Scotland, which is already in level 4 lockdown, recorded the highest number of new coronavirus cases since the pandemic began.
About 100,000 people in Scotland have received a dose of the Pfizer-BioNTech vaccine, which was backed by regulators recently.
The separate OxfordAstraZeneca product has also been approved and is considered to be the game changer.
Scotland will receive 44,000 doses of this vaccine next week.
The priority groups include people administering the jabs, as well as residents in care homes and frontline health workers.
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