Asda will invest at least£150 million to increase its presence within the M25 over the next three years, in an effort to weaken Sainsbury's and Tesco's dominance in the capital.
The Wal-Mart-owned grocer is to open superstores in Romford, Hounslow, Edmonton Green and Feltham, and is seeking planning permission to redevelop its store on the Isle of Dogs.
The expansion marks an accelerated push for Asda, which opened only six London stores in the past five years.
The new stores will create 2,000 jobs and, as part of regeneration developments, Asda will also build residential housing and improve leisure facilities in the area.
A spokeswoman for Asda said: 'There has been a lot of focus on the small stores in London, such as Sainsbury's Local and Tesco Express, but it's only the larger stores that make a difference in terms of regeneration. People will see much more of Asda in London in the next four or five years.'
However, she added that Asda will also grow its share in London by opening smaller supermarkets of between 15,000 sq ft and 25,000 sq ft (1,395 sq m and 2,320 sq m), following the success of a 17,000 sq ft (1,580 sq m) store at Walthamstow.
Asda could not say how many smaller supermarkets it could open in London and said the figure would depend on planning.
The spokeswoman added that the Leeds-based business has a£1 billion investment opportunity in London that could boost its store numbers in the capital from 21 to 70. However, she said land and planning restrictions mean such expansion will not happen overnight.
Asda is also planning to open George standalones in London during the next couple of years.
Sainsbury's remains the dominant grocer in London with about 150 stores, while Tesco has closed the gap recently by acquiring Adminstore and rolling out Express shops.
Asda will open its next London store, part of a£30 million development, on the Old Kent Road on December 13.