Asda, Sainsbury's, Spar, Shop Direct and House of Fraser will all accept mobile payments from next year.
The retailers have teamed with mobile payment innovation Zapp, whose app will allow users to pay for goods and services using just their smartphone and a mobile banking app.
Shoppers would pick up their goods at the store as usual, and when at the checkout would tell the cashier or press a button to signal they are paying using Zapp. After logging into their banking app and selecting which account they want to pay from, a six-digit code for the shopping basket would appear on the phone.
Payment for a low-value amount of shopping can be made simply by waving the phone over a reader without authentication being needed.
Peter Keenan, chief executive of Zapp, said its range of partners "means millions of consumers will be able to shop at tens of thousands of merchants up and down the UK at launch".
Anglian Water, Bristol and Wessex Water and Sutton and East Surrey Water have also signed up for the scheme, meaning some people could be able to pay bills via their mobile.
Discussing what the addition of mobile will mean for business, Rob Harper, head of retail services at PayPal UK, said: “At PayPal we believe in the power of mobile – we’ve helped make mobile payments happen both online and on the high street in the UK, and we handled $27 billion in mobile payments globally in 2013."