The Welcome Break locations will be refitted and rebranded as WHSmith during the year and will be operated on a franchise basis.
The retailer already operates from 259 retail units in airports, rail stations and motorway service areas, along with 543 high street stores.
WHSmith chief executive Kate Swann said: 'We are delighted to be working with Welcome Break to extend our motorway service area offer, bringing WHSmith products and services direct to the motorist.'
Welcome Break chief executive Rod McKie said: 'The last two years have seen significant growth in customer revenues at Welcome Break and this has been due, in no small part, to our introduction of proven high street brands into our motorway service areas. Today's deal with WHSmith represents an exciting further step in this strategy and the partnership will allow us to offer our customers the best in the travel retail sector.'
The motorway stores will offer a range of newspapers, magazines, books and confectionery, tailored to people on the move.