The man was loading his e-cigarette in his bedroom on Saturday in Vilafranca del Penedes, near Barcelona, when the incident occurred, Catalan daily La Vanguardia reported.
According to the local fire service, the device exploded, setting fire to the man's bed. The resulting flames caused burns to the man's arms.
He was then rushed to a nearby hospital for treatment.
The exact cause of the incident is not yet known.
This is not the first time that exploding electronic cigarettes have caused injuries. A man in the UK was killed last week when his e-cigarette 'exploded', apparently igniting oxygen equipment he was using.
Firefighters said the man may have been using a charger that was not compatible with the e-cigarette.