Welcome Break will spend up to £10m on re-branding Coffee Primo shops.
Oxford Services on the M40 and Hopwood Park on the M42 will open before Easter with the rest due to be in business within the next 16 months. Starbucks, which has more than 600 outlets in the UK – including one drive-thru – currently has no shops on motorways.
Welcome Break, which caters for 80m people a year at its 24 sites, also features the brands Waitrose, Burger King and Days Inn.
In August, it will celebrate the 50th anniversary of its first site at Newport Pagnell on the M1. Its Coffee Primo stores already sell 16m cups of coffee a year but the company said it expected the deal with Starbucks to boost sales by at least 30 per cent,
Chief executive Rod McKie said: “This will complement the expansion of the Waitrose estate within Welcome Break and is part of a significant investment by the company.”