Retailers including Asos and New Look have signed up to a new delivery service called Doddle that will place click-and-collect shops in railway stations and other high-footfall destinations.
Travelex founder Lloyd Dorfman and Network Rail have invested £24m in the company, which will create 3,000 jobs.
The company says it will open in 300 locations in the next three years, with London Waterloo - where footfall was in excess of 100 million last year - Bromley South, Brighton, Chelmsford and London Cannon Street the first locations on the list.
Doddle stores will be open seven days a week for shoppers to send and receive parcels. Some will also have changing rooms for shoppers who have ordered clothing, and who will be able to return the parcels straight away if necessary.
Dorfman said: “We intend to take the experience of creating a challenger brand to provide a game-changing service for millions of online shoppers.”