Sadiq Khan has stepped in to intervene on the 427 proposed homes to be built at the Citroen garage site in Capital Interchange Way, after Hounslow Council rejected the plans.
The move he says is in response to the "desperate" need for genuinely affordable housing.
Developer L&Q's plans for the site include 40% affordable homes - 107 shared ownership and 61 based on social rent - a number which Mr Khan plans to boost.
The proposals also include a nursery, retail and office space, and provide an additional 43 new jobs.
The council rejected the proposal due to the negative impact on local heritage sites including Kew Gardens.
Mr Khan said: “I have been clear that I will use the full range of my planning powers to help get London building the new and genuinely affordable housing we so desperately need.
"This rejected application in Brentford already delivers a good number of affordable homes, but by taking it over, it gives me the opportunity to work with the housing association, L&Q, to increase the levels even further.
"I will, of course, weigh up concerns raised about the impact on nearby heritage sites with the pressing need for more new and affordable homes in London.”
The development is in a new "opportunity area" which means it has been identified as having capacity to accommodate around 7,500 new homes and 14,000 jobs.
This is the fifth time the mayor has used the full range of his planning powers to take over applications to boost affordable housing, resulting in 572 more homes for Londoners.
The application will be considered at a hearing in City Hall later in the year.
A spokesman for L&Q said: “We can confirm that the Mayor of London has called in our application to build 427 new homes at the Citroen site in Capital Interchange Way, Brentford.
“We look forward to working with the mayor to bring more high quality, affordable homes to Hounslow.”
There are also plans to build 95 flats with retail space at Wheatstone House in Chiswick High Road.
London Assembly member Andrew Boff has responded with outrage to the mayor's decision.
Mr Boff said: “This call-in amounts to another battle in the mayor's war on the suburbs. It completely neglects and overrides the local council’s decision not to build tower blocks that would negatively impact the environment and local heritage sites.
“It’s disappointing that the mayor has chosen once again to overrule a local council that has raised serious concerns about the proposals.
"I have made it clear in my response to the mayor’s draft London plan that boroughs should not be forced to identify sites for tall buildings, and that boroughs should be supported in setting low to mid rise height limits if they feel this is most appropriate.
“Without clearly setting his policy and parameters beforehand – Khan is completely ignoring local residents' voices.”
Hounslow Council has been approached for a comment.
Keep up to date with the latest news in west London via the free getwestlondon app.
You can even set it to receive push notifications for all the breaking news in your area