The 79 year old singer has been outspoken in his support for Ukraine and supported a family of seven refugees fleeing Russia's invasion by helping them with lodging and bills.
Sir Rod has used the 1991 hit Rhythm Of My Heart, which he has described as a war song, throughout his tours as a dedication to Ukraine.
Before performing the track at Leipzig's Quarterback Immobilien Arena on Friday, he displayed the flag of Ukraine on a projector behind him according to clips on X/Twitter.
The stage then displayed an image of Zelensky on a big screen, while loud boos, shouts and whistles could be heard in videos posted on social media.
Sir Rod made his stance clear in 2022 at a series of shows, telling the PA news agency: "When the war started, in this household we were shocked beyond shock.
"Because I was born just after the war and so my family came through the Second World War, and to see another ground war with tanks, I never thought we'd say the day, it was just shocking and it's just beyond belief now."
He also organised with his family to hire lorries filled with supplies and had them driven to the border of Ukraine, before using the same vehicles to transport a group of refugees to safety in Berlin.
European Union plans to put sanctions on Russia's natural gas sector in response to the Ukraine war, have been controversial in Germany, with reports saying it is blocking the move.
However, Chancellor Olaf Scholz has claimed recently this is not the case.
Sir Rod is set to return to Germany for shows at Hamburg, Cologne and Munich later this month.