Martasidis tested positive for banned substances in a doping control conducted on July 25 in Athens and has had his Games accreditation stripped, the Cypriot Olympic Committee said.
The unidentified Greek competitor's A sample tested positive for banned substances in a pre-Games test also conducted in July in Athens and the athlete has left the Olympic village.
Martasidis, who was to compete in the 85kg category, had arrived in Rio hours earlier only to be informed of a positive test from an out-of-competition doping control, his team said.
These cases bring the number of positive tests announced since the teams arrived in Rio to three, after an Irish boxer was provisionally suspended on Thursday for failing a dope test.
"The leadership of the (Greek) Olympic team in Rio announces the positive first sample of a member of the team during drugs testing conducted in early July in Athens," the Hellenic Olympic Committee (HOC) said of the unnamed competitor.
"The Hellenic Olympic Committee has requested the testing of every Greek athlete taking part in the Games. The specific team member has now left the Olympic village."
The HOC has sent a team of 97 to the Brazilian city for the first Games to be held in South America.
An HOC official told Reuters the test had been conducted on July 5 and the athlete was on the way back to Greece.
He said neither the name of the athlete nor the sport would be made public until the B-sample had been tested or the athlete waived the right for the second test.
The Games officially start later on Friday with the Greek team set to enter the stadium first during the opening ceremony.
(Reporting by Karolos Grohmann; Editing by Alison Williams and Ken Ferris)
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