During a summit meeting the pair said that a direct link between Paris and Barcelona would start on December 15, with a journey time of six hours and 20 minutes.
The Spanish rail operator, RENFE, will work alongside its French equivalent, SNCF, to offer passengers connections between a number of cities.
The Paris to Barcelona service will offer two return trips a day, while there will also be one return trip between Lyon and Barcelona and one return trip between Toulouse and Barcelona.
There will also be one daily return trips between Marseille, Barcelona and Madrid, SNCF said.
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