Health Secretary Matt Hancock said the strategy would save more lives among those most at risk in society.
The move came following advice from the Joint Committee on Vaccination and Immunisation (JCVI).
Two in every five adults have now received at least one vaccine.
The JCVI's advice has been shared with experts leading vaccination programmes in Scotland, Wales and Northern Ireland.
Nadhim Zahawi, minister for Covid vaccine deployment, said this was a very challenging period for people who were homeless.
He added: "We know those experiencing rough sleeping or homelessness are not always able to access healthcare routinely, and therefore can often have a range of health issues which can leave them at an increased risk of this virus.
"Following the recommendation by the JCVI, local teams will now be able to prioritise this group for vaccination alongside priority group 6 and make sure fewer people fall seriously ill or die from Covid-19."
In a letter to the health secretary, experts from the JCVI said people experiencing homelessness had a higher risk of poor outcomes from Covid-19 and high rates of other undiagnosed illnesses.
The team added: "Due to current restrictions, many thousands of people who experience rough sleeping have been accommodated in emergency accommodation.
"This provides a unique opportunity to in-reach vaccination to a population that is otherwise often unable to access basic healthcare."
Housing Secretary Robert Jenrick said that during the pandemic, the government had helped provide accommodation for 37,000 people at risk of rough sleeping.
Jon Sparkes, of the homeless charity Crisis, welcomed the move and said the government should ensure local areas had adequate resources.
He added: "But make no mistake, the vaccine will not make homelessness safe.
"Whether it is living on the streets, or in cars and sheds, or constantly moving between friends' sofas, homelessness is extremely damaging to both your physical and mental health.
"We desperately need a plan to ensure everyone has a safe and secure home."