Police accuse David Sanchez Esteban, a 31-year-old unemployed electrician known as "LOSE" who started painting in 1995, of causing over €31,000 ($42,000) in damages to metro and commuter trains in Madrid.
The Spanish national has also painted trains in London, Copenhagen and Athens, New York and other cities, a police statement said.
"He is considered to be a leader by fans of this type of vandalism as he has painted the most metres of train surface in Spain, which is the criteria they use to establish their seniority," the statement said.
Sanchez was arrested in Madrid on October 28th, a police spokesman said.
Police said he used social network sites to organise meetings with other graffiti artists to prepare raids on trains and upload videos of his exploits.
Sanchez and his crew would activate a train's emergency brake and then spray paint the carriages while the train is stopped on the tracks.
A video posted by police shows a group of over a dozen people, wearing dark clothes and their faces concealed with hoods and scarves, covering the outside of a stopped train in graffiti in less than eight minutes.
In a 2009 interview with Spanish graffiti-makers website Aerosol, Sanchez said the first time he painted a train was "one of the best experiences" of his life.
"I still remember that feeling of cold nerves and adrenaline, all of that mixed with the smell of paint," he said.
"This lifestyle has allowed me to go beyond the boundaries of my neighbourhood and my country, and wherever I go there will always be someone, some contact or some colleague," he added.