Spanish Prime Minister Mariano Rajoy revealed the date for the 6-hour and 20-minute railway service after a Madrid summit with French President Francois Hollande.
The new link will "overcome an historic and geographic barrier", Rajoy said at a joint news conference with the French leader.
Hollande hailed the start of the service as a "great success" but added that "it took 20 years".
The two countries' high-speed networks were linked earlier this year but passengers still had to change trains at Figueres, near the French border, a manoeuvre that added 20 minutes to the journey time.
The final goal is to cut the Paris-Barcelona travel time to 5 hours and 35 minutes once the track from Perpignan to Nimes in southern France is upgraded for high-speed travel.
Spain now boasts 3,000 kilometres of active high-speed lines, the second longest such network in the world.
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