It comes just over a year after the National AIDS Trust won a High Court battle, that confirmed the NHS's legal ability to fund the drug, which can stop people from getting HIV.
The NHS fought not to offer the drug initially, arguing the responsibility for paying for it should be down to local authorities.
A minimum of 10,000 participants will be able to take part in the trial.
Eligible participants for the £10 million trial will be able to access PrEP through sexual health clinics.
The drug is a daily pill which disables HIV before it gets a stranglehold on the body.
Sexual health clinics in London, Brighton, Manchester, Liverpool and Sheffield will be the first to offer PrEP, with the rest of the country taking part by April 2018.
NHS England will use the trial to gather more evidence on how to implement a PrEP programme on a larger scale.
Research suggests that it can cut the risk of being infected with HIV by up to 86%.
Elsewhere in the U.K. - Scotland has announced it will make PrEP available on the NHS, to those at risk of HIV, and in Wales the government is trialling the drug.
The drug is available privately and its use has been linked to the first fall in new infections among gay men.
Simon Stevens, Chief Executive of NHS England said: This major new intervention should complement and supercharge the wide-raging and increasingly successful effort to prevent HIV."
He added: "It's another milestone in more than three decades worth of progress in tackling one of humanity's major health challenges."