The Portuguese driver was among the dead in the accident, which saw the train hit the wall of a bridge and smash into a pillar, according to the mayor of the nearby town of O Porrino.
Pictures posted online and in local media showed one carriage of the train, which was carrying at least 65 people, lying on its side, the front completely caved in and mangled.
A passenger said in a video posted on local daily La Voz de Galicia that the train suddenly started wobbling.
"It wouldn't stop. I was sitting down and I fell to the ground," she said.
"And then the train stopped. It was that quick."
Ramon Gonzalez, a witness interviewed by Spanish television who works in the station cafeteria near the accident, said there was a "very strong bang."
"It was full of black smoke ... It's a straight line, the train was due to stop in 50 metres, so this isn't normal.
The train was travelling from the Galician town of Vigo to the city of Porto in Portugal when the accident happened near O Porrino.
Manuel Carrera, deputy mayor of O Porrino, said four people had died in the accident.
Adif, the company that manages railways in Spain and is in charge of the tracks, said the accident happened around 9.30am local time just before arriving into the station.
"It's a very straight line," a spokeswoman said.
"There isn't bad visibility there, it emerges from a curb," Eva Garcia de la Torre, Mayor of O Porrino, told the Cadena Ser radio.
But the reason of the derailment has yet to be determined.
Spain's railway company Renfe said the train and the driver were both Portuguese, adding that railway traffic had been suspended in the area.
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