The Italian man, sought by Interpol for the grisly murder, was discovered at a campsite on the outskirts of Rome, and taken to prison to await extradition to France.
At the time of the murder Venezuelan police said the suspect was the butler of the victim, Paul Maurice Wolnerman, 71, who was shot dead on April 2012 in the port city of Lecheria.
Another suspect, Wolnerman's driver, was arrested in Venezuela in 2012 and admitted participating in the murder. Police described him as the "direct author" of the crime.
Wolnerman, who had lived in Venezuela since 2005, had decided to sell his penthouse, car and motorboat and move to the Dominican Republic with his butler, according to the investigation.