The country was in mourning over Wednesday's horrific tragedy, which police said had killed 78 people including foreigners and left many more injured.
The 52-year-old driver faces criminal accusations including "recklessness" over the crash near the pilgrimage city of Santiago de Compostela, said Jaime Iglesias, police chief in the northwestern Galicia region.
The grey-haired driver, who reportedly boasted of his love for speed online, was detained Thursday in hospital where he had been under police surveillance, Iglesias told a news conference.
A Spanish judge had ordered police to question the man, identified as Francisco Jose Garzon Amo in local media, which published photographs of him with blood covering the right side of his face.
He has not been charged with a crime and has yet to be quizzed by police about the tragedy.
Spain's leading El Pais newspaper said the driver of the train -- which was carrying over 200 passengers and crew -- had been unable to brake in time.
Seventy-eight passengers perished, six of whom have yet to be identified, according to a revised police toll.
Four foreigners are among the dead -- an American, an Algerian, a Mexican and a French national, local officials said.
Iglesias said forensic police were working with "mangled bodies", some of which were difficult to identify because of their injuries.
The crash also injured more than 100 people, a number of whom remain in serious condition in hospital including three children, Galicia health services said.
Most of the injured are Spanish but at least eight were foreigners from Argentina, Britain, Colombia, the United States and Peru.
A dramatic 10-second video from a railway security camera appears to show the train rocketing around a curve, slamming into a concrete wall at the side of the track as the engine overturned.
Carriages piled on top of each other in a smouldering wreckage of mangled steel, with one carriage flying into the air before coming to a rest on top of a six-metre (18-foot) siding.
Smoke billowed from the gutted cars as bodies were strewn across the tracks.
The driver, while still trapped in his cab, told railway officials by radio that the train had taken the curve at 190 kilometres (118 miles) an hour, unidentified investigation sources told El Pais, more than double the 80 kph speed limit on that section of track.
"I was going at 190! I hope no one died because it will weigh on my conscience," he was quoted as saying.
El Pais said the driver told them a speed alarm had been activated on his control panel, adding:. "He tried to brake without being able to avoid the tragedy."
He had been with state rail company Renfe for 30 years and had 13 years' experience as a driver.
Media reports described Garzon Amo, one of two drivers on the train, as a speed freak who once gleefully posted a picture on his Facebook page of a train speedometer at 200 kph.
A caption read: "I am on the edge, I can't go faster or else I will be fined."
Spanish newspapers quoted another of his posts as saying: "What fun it would be to race the Guardia Civil (police) and pass them, causing their radar to blow up hehehe. What a huge fine that would be for Renfe."
The Facebook page has since been taken down.
Secretary of state for transport Rafael Catala said the crash "seems to be linked to excessive speed" but that he was awaiting the findings of the judicial probe.
Renfe said the train -- a model able to adapt between high speed and normal tracks -- had no technical problems and had just passed an inspection on the morning of the accident.
Experts have raised questions about the track's speed signalling system.
Since high-speed trains use the route, it has been equipped with an automatic speed control system known as the European Rail Traffic Management System (ERTMS), under which a train's brakes can be automatically applied if speeding.
But the secretary general of Spain's train drivers' union, Juan Jesus Garcia Fraile, told public radio the system was not in place at the crash site.
The high-speed track linking Ourense, Santiago de Compostela and La Coruna in Galicia is one of Spain's newest, having been inaugurated in December 2011.
Prime Minister Mariano Rajoy, a native of Santiago de Compostela, declared three days of national mourning after visiting the scene Thursday.
It was Spain's deadliest rail accident since 1944 when hundreds were killed in a train collision, also between Madrid and Galicia. In 1972, 77 people died when a train derailed between Cadix and Seville.
Many of the passengers were thought to be on their way to a festival in honour of Saint James, the apostle who gave his name to Santiago de Compostela, an annual event that draws crowds of pilgrims to the town.
All festivities have now been cancelled.
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