"Today we have an important result for the air coalition: Greece will take part in training our pilots on F-16s. Thank you for this offer," Zelensky told media alongside Mitsotakis on an official visit to Athens.
Kyiv on Friday welcomed a US decision to let Denmark and the Netherlands hand F-16 fighter jets over to Ukraine once its pilots are trained to use them.
Training by an 11-nation coalition is to begin this month, and officials hope pilots will be ready by early 2024.
Greece has been a strong supporter of Ukraine since Russia's invasion, providing humanitarian aid and weapons including infantry fighting vehicles, Kalashnikov assault rifles, launchers and ammunition.
Mitsotakis on Monday said Greece would "be present in the titanic effort to reconstruct and rebuild" Ukraine, with "particular emphasis on Odesa."
The Ukrainian port city in the early 19th century was the birthplace of a secret Greek revolutionary organisation that helped to spark the 1821 revolution against Ottoman rule in Greece.
Zelensky is concluding a European tour with previous stops in Sweden, the Netherlands and Denmark.
His visit to Athens coincided with an informal dinner hosted by Mitsotakis with Balkan leaders, European Commission President Ursula von der Leyen and European Council chief Charles Michel.
The Greek PM's office said the gathering marks the twentieth anniversary of the 2003 Thessaloniki summit confirming the European perspective of Western Balkan states.
The Ukrainian president had earlier posted on Telegram that he would hold a joint meeting and separate talks on bilateral issues with the Balkan leaders, and also meet with the European Commission president.
The other participants are the presidents of Serbia, Moldova, Montenegro and Romania, the prime ministers of Kosovo, North Macedonia, Bulgaria and Croatia, and the chairwoman of the council of ministers of Bosnia and Herzegovina, Mitsotakis' office said in a statement.
A historically Russian ally bound by centuries of tradition and a shared Orthodox Christian faith, Greece under Mitsotakis has shifted and unequivocally condemned Moscow's invasion of Ukraine.
Last year it expelled a dozen members of Russia's diplomatic and consular missions, and is hosting thousands of Ukrainians and their families.
In April, Ukrainian Defence Minister Oleksii Reznikov visited the Greek capital for talks with his then counterpart Nikos Panagiotopoulos.
Reznikov at the time said Ukraine after the war would seek Greek assistance in de-mining the Sea of Azov, and developing the country's naval forces.
Greece has also offered to rebuild the maternity hospital in Mariupol that was shelled last year.
In April 2022, Zelensky gave a televised speech at a special session of Greek parliament to request assistance for Mariupol and Odessa, two Ukrainian cities that have had large ethnic Greek populations for centuries.
The session saw a rare attendance by the Greek head of state President Katerina Sakellaropoulou, and Zelensky was given a standing ovation by Greek ministers and MPs.
The Greek communists and a small nationalist party boycotted the event.
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