It comes as official figures show infection rates are rising in all age groups – including the over-70s.
The rollout follows recommendations from the UK’s vaccine advisers who say additional jabs will help boost protection for the most vulnerable.
Spring boosters are already being rolled out in Wales and Scotland.
A wider booster programme – involving more people – is expected this autumn.
While vaccines have been shown to provide good protection against severe disease, protection wanes over time.
And as many of the oldest received their last jab in autumn 2021, their immunity may now be declining, experts say.
Now, a second booster – to be administered six months after the previous dose – will be offered to:
About five million people in the UK will be eligible to book the extra booster jab – with the first 600,000 people to be invited from this week.
Dr Nikki Kanani, GP and deputy lead for the NHS’s vaccination programme, urged everyone eligible to book their boosters as soon as possible.
She said: “With infections rising this is a really important opportunity for people who are eligible to come forward and get booked and get their spring booster.”
The extra jabs will be given around six months after the last dose of vaccine.
Across the UK more than two-thirds of people aged over 12 have had two Covid vaccines plus a single booster jab.
A first booster dose is currently available for everyone aged 16 and over, and at-risk children aged 12 to 15.
But up until now only people with severely weakened immune systems had been eligible for a fourth dose – three doses plus a booster.
The Joint Committee on Vaccination and Immunisation has suggested further boosters will be offered to a wider group of people in autumn.
Experts believe winter is likely to be the season when the threat from Covid is greatest – for individuals, the NHS and care homes.