The train was travelling from the Galician town of Vigo to the city of Porto in Portugal when the accident happened near the town of O Porrino.
Authorities in Galicia said three people were killed in the three-carriage train, which was carrying some 65 people.
Footage of the wreck showed one carriage lying on its side, the front of the train completely caved in and mangled.
Helicopters and ambulances rushed to the scene to attend to the victims.
"It's a very straight line," a spokeswoman said.
Pictures posted in local daily La Voz de Galicia showed doctors attending to passengers on the station platform.
Ramon Gonzalez, a witness interviewed by Spanish television, said there was a "very strong bang."
"It was full of black smoke," he said over the phone.
"It's a straight line... So this isn't normal.
"There are still some injured here but very not serious, the seriously injured were quickly evacuated."
Local media said the driver was among the dead, but authorities have yet to confirm this.
Galicia was also the scene of one of Spain's worst rail disasters in 2013, when around 80 people were killed and another 144 injured after a train slammed into a concrete wall on the outskirts of Santiago de Compostela.
The train was approaching a curve at more than twice the speed limit on that piece of the track in Galicia.
The driver of the train has been charged with negligent homicide and released without bail pending trial. He is the only person to face criminal charges over the accident.
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