Concourse facelifts are to be carried out at Birmingham New Street, Manchester Piccadilly, London Waterloo and London King's Cross.
Birmingham's new concourse will add 16,000 sq ft of retail space by 2014, while upgrading an existing mezzanine at Manchester Piccadilly will add 12,000 sq ft, currently earmarked for restaurants, from spring next year.
Waterloo's central concourse retail units currently held by WH Smith and Tie Rack will disappear, with 20,000 sq ft of balcony-level retail space created instead by spring 2012. King's Cross's facelift, also to be completed by spring 2012, will add 16,000 sq ft of new shops.
More than 300 retailers gathered in London this week to listen to the plans for some of the UK's highest footfall areas. Network Rail, which owns the stations, revealed that combined annual footfall at the four sites was now more than 240 million.
Deals for the extra units, which equate to around 15% of Network Rail's current 480,000 sq ft of retail space across 18 stations, will generate more than £1bn for the rail company over the next five years.
"Through working proactively with retailers we will be able to offer a great customer experience and create destination stations where people go to shop, meet and eat," said Gavin McKechnie, head of retail at Network Rail.