The programme, which will offer tests to thousands of adults per day, aims to improve understanding and gain "vital" data about antibody protection following Covid infection and vaccination.
From Tuesday, anyone over 18 from any of the four UK nations can opt in to the programme when receiving a PCR test.
Of those who test positive for coronavirus, up to 8,000 will be sent two finger prick antibody tests to complete at home and send back for analysis. The first must be taken as soon as possible after the positive result, and the second must be taken 28 days later.
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The UK Health Security Agency, which is running the programme, will work alongside NHS test and trace services in England, Scotland, Wales and Northern Ireland and use the results to monitor levels of antibodies in positive cases across the UK.
The Department of Health and Social Care says it will be the first time antibody tests have been made available to the general public, and the scheme could also provide insight into any groups of people who do not develop an immune response.
The data will be used to inform the ongoing approach to the pandemic and give further insight into the effectiveness of vaccines on new variants.
He said: "Our new national antibody testing will be quick and easy to take part in. By doing so you'll be helping strengthen our understanding of Covid-19 as we cautiously return to a more normal life.
"I'm proud to see all parts of the UK uniting around this new initiative and working together to arm ourselves with even more valuable insights into how Covid-19 vaccines are protecting people up and down the UK."
Those taking part must take the first antibody test as soon as possible after receiving a positive PCR result so the body does not have time to generate a detectable antibody response to the infection.
The second test should be taken 28 days later and will measure antibodies generated in response to the infection.
UK Health Security Agency chief executive Dr Jenny Harries said: "We are rolling out antibody testing across the UK to gain vital data into the impact of our vaccination programme and on immune responses to different variants of Covid-19. This innovative programme is only possible thanks to the thousands of people who continue to help with studies on vaccine and treatment effectiveness each week."
The announcement comes amid ongoing debate over the rollout of booster jabs in the UK.
Dr Chris Smith, consultant virologist and lecturer at Cambridge University, warned the UK must not take its "eye off the ball" with Covid-19 vaccinations and that the virus could come "roaring back".
Dr Smith said a decision on booster jabs should not be "rash, (or) rushed", and that the Government is considering a more "strategic" approach.
Mr Javid has said he is "confident" a booster vaccine campaign can start next month despite reports that experts want more time to consider whether they are needed.
The Government said a further 104 people had died within 28 days of testing positive for Covid-19 as of Saturday, and there had been a further 32,058 lab-confirmed Covid-19 cases in the UK.
Speaking on BBC Breakfast, Dr Smith said: "We all agree that (the pandemic) is not over until it is over in every corner of the world, because otherwise it will just come roaring back.
"But one must not take one's eye off the ball here because it would be very easy to unstitch all of the good work we've done so far if it turns out with time we do lose immunity because the vaccines wane in their effectiveness.
"As we go into winter, now is a critical period and I think that is why we haven't seen a rash, rushed decision by the JCVI (Joint Committee on Vaccination and Immunisation) and the Government."
He added: "While other countries are embarking on booster programmes, people are taking stock, they are looking at the data and maybe making a decision on how to intervene strategically in certain groups."
Research by the National Office for Statistics (ONS) recently found more than three-quarters of adults in every age group say they would be likely or very likely to get a booster jab if offered.
Overall, 87 per cent of adults surveyed by the ONS said they would be likely or very likely to get a third coronavirus jab.
Likelihood increased with age, with 96 per cent of those aged 70 and over indicating their interest, down to 78 per cent of 16 to 29-year-olds.