From 5 January, 2014, the French operator will introduce a weekly sailing between Poole and Gijon.
It already serves Gijon from the French port of Nantes-St Nazaire.
The Poole-Gijon service will leave the Dorset port on Tuesdays with the return leg departing from Spain on Fridays.
LD Lines will next month also launch the "first-ever ferry link between Ireland, Western France and Northern Spain," connecting the ports of Rosslare, St.Nazaire and Gijon with a weekly round trip, effective 7 January 2014.
The new routes will be served by the Norman Asturias and its sister ship Scintu which each offer of capacity for up 110 freight vehicles or 150 trailers.
Expansion follows "positive early haulier response" to the company's new Poole-Santander route with freight traffic ultilisation of up to 90% since the service commenced in early November.
The service operates from Poole on Saturdays and returns from Santander on Sundays, by-passing the weekend HGV driving ban in France, LD Lines underlines.
"The additional services will further expand our Atlantic network by providing improved transport links between the UK, Southern Ireland, Spain, France and Portugal and give new and existing customers greater choice," said LD Lines'CEO Christophe Santoni.
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