The upmarket supermarket intends to diversify its offering to boost profits.
The new venture will be trailed at two sites, Watford and Bayswater, in west London. If these sites prove successful, it could potentially lead to the roll out of around 100 Little Waitrose stores at Shell garages across the country.
Waitrose is hoping to capture an untapped market – customers who want to buy its products but live too far away from its shops.
Waitrose's fresh expansions into convenience stores will hot up competition in the sector with its supermarket rivals.
Sainsbury's recently opened its 400th Sainsbury's Local shops and Morrison's is also making a concerted push into the sector.
Waitrose's move into the convenience store business began earlier this year with the opening of several small shops in the UK, including one on London's Old Brompton Street.
It plans to launch more than 40 smaller-format stores by the end of the year.
Waitrose currently has 263 supermarkets and is trailing alternative revenue streams, such as supplying its branded sandwiches to Boots stores.
Waitrose will report its half-year results this week.
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