Over the next three years, the two firms plan to create 150 Tesco Express-Esso partnership sites across the UK.
The forecourts will continue to carry the Esso name while the shops will be called Tesco Express.
The scheme has already been piloted at eight petrol stations.
The mini-supermarkets sell a wide range of groceries and are open 24 hours a day.
'Outstanding success'
Tesco chief executive Terry Leahy said: "We have developed an excellent relationship with Esso. I am delighted we'll be creating up to 4,000 good jobs in an exciting industry.
"Tesco Express is an outstanding success with customers," he added.
The Tesco Express format has also been tried out at 16 of Tesco's own petrol stations.
A spokesman for Tesco declined to say how much the investment would cost and said although the contract was not yet signed it was purely a formality.
The deal is Tesco's latest move in its battle with other major supermarket chains for market share.
The company has revamped its image in recent years and succeeded in overtaking former market leader J Sainsbury to the top spot.
The announcement comes hot on the heels of news that the company plans to create 7,000 jobs this year with the expansion of its home shopping service.
The group said it would triple the number of stores offering internet shopping after research showed "enormous demand" for Tesco Direct.