London mayor Sadiq Khan said the Greater London Authority will provide £600,000 to establish at least three hubs that will aim to boost take-up of early-years education and childcare support entitlements, and enable more parents to seek work.
The hubs, which will be funded for three years, may also provide childcare out of normal working hours and support children with special educational needs and disabilities, as well as promoting careers in early-years education.
City Hall will begin an open application process next month to select the lead organisation for each of the hubs, and will develop a toolkit to share learning across the capital.
Khan, who outlined the plans earlier this year, said: "London has some of the best schools in the world, and we know that the earlier a child starts to learn, the better they tend to do later in life.
"There is already great work going on but we need to give all young Londoners the chance to succeed, no matter what their background, and raise the quality of our education system even higher to compete with other global cities.
"By increasing access to good quality, affordable early years education and supporting pupils from disadvantaged backgrounds, we can help ensure no child is left behind.
"But proposed funding cuts, coupled with existing budget pressures, mean we will lose teachers, risk falling standards, and pupils will suffer. I will continue to fight for a fairly funded school system that will work for young Londoners for generations to come - no matter what their background."
Joanne McCartney, deputy mayor for education and childcare, said: "A child's first years affect the rest of their life, and it's vital that good quality, affordable childcare and early-years education are available to all.
"Childcare can become a costly barrier to employment for some parents, and by bringing organisations together to provide this support, we can help ensure parents are aware of what's available and increase take-up of the free early-years offer across London."