The Labour leader will be in Stevenage on Thursday urging the Government to use thousands of pharmacies to help deliver round-the-clock coronavirus vaccinations.
Keir Starmer will visit Robertson House, one of the country's first seven centres for mass vaccination, which opened on Monday.
The centre will initially be used to inoculate those who are aged 80 and over.
Nurses, doctors and other NHS staff working nearby will also be vaccinated there, along with social care and care-home workers.
Sir Keir is calling for a 24-hour vaccine programme to be rolled out by the end of February, to help deliver four million vaccines every week.
He's urging ministers to use England's 11,500 community pharmacies, to guarantee vaccines can be delivered on every high street.
The whole country wants this rollout to succeed. We were the first to get the vaccine and if we get this right and pull together, I know we can be the first country to roll it out successfully.
"To do that, the Government needs to match the nation's ambition with a 24/7 rollout which harnesses all the expertise and dedication our country has to offer", Sir Keir added.
"Every high street has a pharmacy and I want to see every possible pharmacy deployed to help.
"Labour will play our part. Labour councils are already stepping up, supporting their communities and making generous offers of support to the Government.
"Across those communities, pharmacists stand ready to play their part too. Let's use them, and let's vaccinate Britain."
Prime Minister Boris Johnson told MPs on Wednesday that the NHS will launch a round-the-clock vaccination service as soon as possible, despite Downing Street previously saying there was no clamour for a 24/7 model.
The Government also said they are considering what further role community pharmacies can play.
Health Secretary and West Suffolk MP, Matt Hancock, said on Monday that 200 community pharmacies are coming on stream for vaccinations "very shortly".