Twenty-seven third country nationals, all from Asian countries, were found packed in a truck with Bulgarian licence plates, which was stopped by police after a brief chase in the northwestern city of Arta.
The vehicle's driver initially tried to avoid a routine traffic check, it was announced on Monday.
The driver was able to flee but his co-driver, a foreign national, was arrested.
During questioning it was established that the foreign nationals, 13 of which held valid ID documents, had paid 3,000 euros for transport from Athens to the NW seaport of Igoumenitsa, and a subsequent attempt to try and board an Italy bound ferry boat.
The migrant smuggler and the 14 illegal migrants were led before a prosecutor while the truck was impounded.