Some High Street pharmacies in England will start vaccinating people from priority groups on Thursday, with 200 providing jabs in the next two weeks.
Six chemists in Halifax, Macclesfield, Widnes, Guildford, Edgware and Telford are the first to offer appointments to those invited by letter.
But pharmacists say many more sites should be allowed to give the jab, not just the largest ones.
More than 2.6 million people in the UK have now received their first dose.
Across the UK, the target is to vaccinate 15 million people in the top four priority groups - care home residents and workers, NHS frontline staff, the over-70s and the extremely clinically vulnerable - by mid-February.
The vaccines - made by either Oxford-AstraZeneca or Pfizer-BioNTech - are being administered at hospitals, care homes, GP surgeries and vaccination centres.
It comes as the UK saw its highest number of daily reported coronavirus deaths since the pandemic began, with the government announcing a further 1,564 deaths of people within 28 days of a positive Covid test.
On Wednesday evening, the Scottish government published its detailed 16-page plan for rolling out the vaccine, including details of how many vaccines it expects to receive every week until the end of May.
The first pharmacy sites in England to deliver a vaccine have been chosen because they are capable of delivering large numbers of vaccines quickly while allowing space for social distancing.
- Boots, Halifax
- Andrews Pharmacy, Macclesfield
- Appleton Village Pharmacy, Widnes
- Superdrug Pharmacy, Guildford
- Cullimore Chemist, Edgware
- Woodside Pharmacy, Telford
People will be invited by letter to make an appointment at one of the pharmacies, or a vaccination centre, through the NHS Covid-19 vaccination booking service.
Anyone who doesn't want to travel to these sites can still be vaccinated by their local GP or hospital service, but they may have to wait longer.
Up to 70 more pharmacies will be taking bookings for appointments for next week, with 200 in total offering slots over the next fortnight, according to NHS England.
Vaccines are currently being offered at more than 1,000 sites, including :
- 200 hospitals
- 800 GP-led services
- seven mass vaccination centres, one in each English region
An Asda supermarket in Birmingham will also host a vaccination centre, with pharmacy staff giving jabs in the store's former clothing section from 25 January.
But the National Pharmacy Association says the rules on which pharmacies qualify to deliver Covid vaccines should be relaxed to allow more to take part.
At present, pharmacies have to be able to deliver 1,000 vaccines a week, have enough fridge space to store all the doses, and be able to open seven days a week.
Andrew Lane, of the National Pharmacy Association, said now that the Oxford vaccine had been approved, community pharmacies could store and administer it in the same way as they deliver the flu jab.
The Oxford vaccine only needs to be stored at fridge temperature, as opposed to the freezer temperatures of -70C required by Pfizer.
"We're here, we're trained, we will deliver," said Mr Lane, who represents Buckinghamshire, Oxfordshire, Berkshire and Northamptonshire.
NHS England has said that as more supplies of vaccine become available, more community pharmacists will be able to play a role in the programme.
'Working flat out'
The government's vaccines minister Nadhim Zahawi said staff across the NHS had "pulled out all the stops to help ramp up vaccinations" and were working day and night to keep people safe.
Prof Claire Anderson, chair of the Royal Pharmaceutical Society's English Pharmacy Board, said pharmacy teams in hospital, primary care and the community were "working flat out to support the nation's health".
She said she looked forward to the vaccination programme being expanded through pharmacies to benefit patients.
Boris Johnson said on Wednesday that vaccinations would also start being offered 24 hours a day, seven days a week "as soon as possible" - but supply of doses was currently the limiting factor.
It comes as hospitals struggle to cope with the rising numbers of patients being admitted with Covid.
A study published today has shown the impact of packed intensive care units on death rates, finding that patients in England's busiest ICUs in 2020 were 20% more likely to die.
Meanwhile, a government committee is meeting later to discuss whether to stop flights from Brazil coming to the UK because of concern about a new variant of the virus believed to have emerged there.
Arrivals from Brazil already have to self-isolate for 10 days.
The strain is one of a small number of new variants which have been spreading, including ones first spotted in the UK and South Africa.
Scientists are racing to understand what it means for the vaccines - but most experts think vaccines will still be effective.
In other developments:
- Most people who have had Covid-19 are protected from catching it again for at least five months, a study led by Public Health England shows
- The UK's new testing rule for arrivals has been pushed back by a few days to give travellers more time to prepare, the government has said. Arrivals to the UK must be required to show proof of a negative test from 04:00 GMT on Monday
- Some rail services in England are being cut during lockdown, with passengers urged to check train times