The European football governing body's decision comes just 24 hours after the Hellenic Football Federation (EPO) issued points deductions to Volos and another club, Kavala, before the start of the Super League season for their role in the scandal.
Volos will start the new campaign on -10 points and Kavala on -8 points.
"Olympiakos Volos FC have been excluded from this season's Europa League and given a further three-year ban from UEFA competition, deferred for a probationary period of five seasons, after breaching Article 5 of the UEFA Disciplinary Regulations," UEFA said in a media statement on Thursday.
Under UEFA rules, any points-deduction punishment implies a club's exclusion from European competition.
"The decision was taken by the UEFA Control and Disciplinary Body. The Greek club have until midnight on Monday to submit an appeal under Article 49 of the UEFA Disciplinary Regulations." the statement continued.
"The UEFA administration will decide which club will replace Olympiakos Volos in the UEFA Europa League, where they were scheduled to face Paris Saint-Germain in the play-offs on August 18 and August 25."
Club lawyer Michael Mitzikos said: "We will appeal first to UEFA's appeal's body and will also consider measures with the CAS (Court of Arbitration for Sport)."
Last month, the disciplinary of the Super League had voted to relegate both clubs to the second division. However, both teams appealed that decision with the federation leading to Wednesday's reprieve for the clubs.
The decision to allow Olympiakos Volos, who were making their debut in European competition, and Kavala to remain in the Super League means Larissa and Panserraikos, who were in line to replace them, will stay in the second tier.
