Asda has confirmed plans to buy 132 sites from The Co-op in a deal worth £600million.
The purchase includes 129 retail stores with attached petrol stations, plus three development sites.
The 2,300 members of staff currently employed in the Co-op stores will transfer over to Asda.
Asda says the sites are located nationwide, with the supermarket to create a new "distinct format fin the convenience market".
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Asda will pay £438million in cash and take on around £162million of lease liabilities as part of the deal.
The final amount - which will be funded by through a combination of existing cash resources and bank finance -will be confirmed when completed.
Asda is owned by billionaire brothers Mohsin and Zuber Issa.
The pair started off in business by founding Euro Garages with a single petrol station in Bury, Greater Manchester, before building it up to form a network of forecourts across the UK.
They formed EG Group with the backing of TDR Capital and expanded into Europe before the brothers and the private equity firm teamed up to buy Asda in 2020 for £6.8billion.
EG Group now owns 6,000 forecourts, as well as various fast food brands in Europe and the US.
Mohsin Issa, Co-owner of Asda, said: “We have always been clear in our ambition to grow Asda and are hugely excited to create this new and distinct part of our business.
“We see convenience as a significant growth opportunity for the business.
“This acquisition accelerates our strategy in this area and forms part of our long-term ambition to become the UK’s second largest supermarket.
“We look forward to welcoming the Co-op colleagues to this new part of our business after we complete the transaction and due processes in the coming months.”
The Co-op Group said the forecourts it is selling make up 5% of its retail estate of 2,564 stores.
Shirine Khoury-Haq, the Co-op’s newly appointed chief executive, said: “This transaction is in line with our strategy to move away from operating petrol forecourts and supports our vision of co-operating for a fairer world while building our core leading convenience business.”
The news comes after the Co-op announced it was scrapped use-by dates on its yoghurts - telling customers to use their common sense instead.
The Co-op will be keeping best-before dates on its own yoghurts instead.
Nick Cornwall, head of food technical at the Co-op, said yoghurt is mostly fine to eat after the use-by date, provided it has been kept unopened in a fridge.