The Ukrainian leader physically recoiled as the French President leaned in for an intimate photo opportunity at a press conference in Kyiv.
Pictures from the scene show the two men in an awkward embrace, with Mr Macron's repeated attempts to engage in a hug rebuffed.
Instead, Mr Zelenskyy simply pulls away, looks awkwardly to his right and pats the 44-year-old on the back.
The images have caused a sensation online, with several commentators quick to mock the humiliated Frenchman.
The awkward embrace has caused a stir online
LUDOVIC MARIN
Mr Macron met with Mr Zelenskyy in Kyiv
VALENTYN OGIRENKO
Tory MP Johnny Mercer, sharing the image online, wrote: "In politics you have two sorts of people.
"Those who want to do something, or those who want to be someone.
"I've never seen it encapsulated so well in one photo."
Fellow Conservative MP Michael Fabricant piled in: "Although visiting two months later than Boris Johnson, Macron goes one step further by sticking his tongue into Volodymyr Zelenskyy's ear. You can't beat that."
Commentator Anthony O'Neill said: "These photos say it all, don't they. Macron's hug is rejected.
"Macron is treating Zelenskyy as a photo opportunity and offering him zero help on the battlefield."
While ABC's James Longman added: "More classic Macron PDA."
During the trip to the Ukrainian capital, Mr Macron joined European Union leaders in making assurances to Mr Zelenskyy over the country's proposed EU membership bid.
France, Germany, Italy and Romania insist Ukraine should be given "immediate" candidate status following its application.
The horrors of war were laid bare to the group, as they visited the nearby town of Irpin – that had been occupied in the earlier conflict.
Mr Zelenskyy patted Mr Macron on the back
LUDOVIC MARIN
Confronted by a scene of utter devastation, Italian Prime Minister Mario Draghi said: "We will rebuild everything.
"They destroyed kindergartens, they destroyed playgrounds. Everything will be rebuilt."
The awkward pictures of the Ukrainian leader's embrace with the French President may come as no surprise to some, given their often tricky relationship.
Mr Macron has been widely accused of being an apologist for Russian President Vladimir Putin in the West.
