The President and First Lady discuss their two-decade marriage and being separated from their two children since the war with Russia began.
Zelenska was also named Vogue’s latest digital cover star, with the portrait of her shared to social media called ‘portrait of bravery’.
"As the war in Ukraine enters a critical new phase, the country's First Lady, Olena Zelenska, has become a key player - a frontline diplomat and the face of her nation's emotional toll," Vogue said on its Instagram post.
The first photo if Zelenska shows her sitting in the Presidential Office, while other photos show the First Lady posing among wreckage from the war and features soldiers in the background.
The pair were interviewed in Kyiv, and the full profile of Zelenska will be published in the magazine’s October issue.
While some on social media have praised the images a s”powerful”, others have taken issue with the couple doing a photoshoot in the middle of a war.
"During a war, you either shoot your opponent or get shot...by Vogue," a Twitter user commented.
"Priorities. I'm sure the dudes in the trenches appreciate the effort the Zelensky's are putting into stopping the war. A Vogue cover will help, for sure. Slava Ukraini," tweeted another.
