The mayor of London expects the site to deliver at least 200 homes, with 50% being social rented or other genuinely affordable housing.
Construction of the homes is expected to begin before March 2022.
The 1.4-hectare site’s current facilities, including a car park, offices and hospital testing facilities, will be relocated to other parts of the hospital.
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“Under Sadiq, City Hall is taking a far more active approach to unlocking sites across the capital,” said James Murray, deputy mayor for housing and residential development.
“We are using the land fund he established to buy sites like this one in Enfield, where we will be able to build genuinely affordable homes while protecting healthcare for the local community.”
Maria Kane, chief executive at NMUH NHS Trust, added: “We’re looking forward to working with the Greater London Authority to make best use of the land so that it better meets the needs of people who use the hospital and benefits our local community.”