The statue, one of two best actor trophies won by Penn in 2004 and 2009 respectively, will stay in Ukraine until the end of the war.
The presentation happened during Penn’s third visit to the country during the full-scale war.
During their meeting, the actor was presented with the Order of Merit of the III degree by Mr Zelensky, who thanked him for his “significant contribution” to the war effort.
Penn was also honoured by having his name placed on a stone on the Walk of the Brave, which recognises “brave people who have stood with Ukraine from the very beginning”.
His name will feature next to the list of many world leaders who have helped Ukraine during the conflict.
A post on Mr Zelensky’s Instagram page read: “American actor and film director Sean Penn @seanpenn came to Ukraine for the third time during the full-scale war already.
“This time our meeting was special. Sean brought his Oscar statuette as a symbol of faith in the victory of our country. It will be in Ukraine until the end of the war.
“It was with great pleasure that I presented Sean Penn with the Order of Merit of the III degree. Thank you for such sincere support and significant contribution to the popularization of Ukraine in the world.”
Penn fled Ukraine in March while filming a documentary about the conflict.
The presentations come as the actor is due to be honoured with the Bob Hope Humanitarian Award by the Television Academy.
He is due to be recognised for his “decades of activism” at the organisation’s 26th Hall of Fame next week on November 16.