The inaugural service, a German ICE train, left the French capital's Gare de l'Est station at 9:55am and was due at Berlin Hauptbahnhof at 6:03pm.
The service shaves only minutes off the fastest one-change connection between both capitals.
The trains run at up to 320 kilometres per hour while in France, but that speed drops to a maximum 250 km/h in Germany -- only just meeting the definition of high-speed rail travel.
A one-way ticket for the 1,100- kilometre journey costs upwards of €99, rising sharply on busy days.
READ ALSO: What to know about new daytime high speed Paris-Berlin train service
Budget airlines, such as easyJet, charge around half that for a 1h45 nonstop flight between both capitals.
But French rail operator SNCF has reported an occupancy rate of over 80 percent for the new trains.
"Bookings are going very well," said SNCF boss Jean-Pierre Farandou. "People like to travel in comfort rather than negotiating the sometimes difficult access" to airports, he said.
Lea Bader, who travelled on Monday's train, said she did not hesitate to take the train because she would have had to buy an extra ticket for her cello on a plane.
She said the train was also more comfortable, and she welcomed the absence of a need to change trains which she said had been "horrible, because each time there was a problem or a delay".
A third of Germany's high-speed train services suffered delays in 2023, and line closures because of repairs or maintenance work are commonplace.
Kevin Kern, a 33-year-old Berliner, said his main motivation for rail travel is "the environment", with the trip generating an estimated 100 times less CO2 emissions per passenger than taking the plane.
SNCF and Deutsche Bahn together account for 30 million journeys between France and Germany.
SNCF's Farandou meanwhile said he was "perfectly confident" that the new daytime service will not see the same problems as a night service between Paris and Berlin relaunched a year ago after a near-10-year pause.
The night service has been dogged with delays, and was even halted completely between August and October of last year because of railway work done on the German side.
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