The pair were pictured together for the piece by renowned photographer Annie Leibowitz - although the article primarily concentrated on Zelenska, 44.
It's called: "Portrait of Bravery: Ukraine's First Lady Olena Zelenska."
Following the piece's publication, conservative pundits and politicians seized upon the photo shoot as proof that the United States should not have sent $40 billion in assistance to Ukraine to help its war effort against Russia.
Republican Congresswoman Lauren Boebert tweeted a photo of Zelensky and Zelenska together while declaring: "While we send Ukraine $60 billion in aid, Zelensky is doing photoshoots for Vogue Magazine. These people think we are nothing but a bunch of suckers."
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The article was written by Paris-based journalist Rachel Donadio. On Twitter, Donadio referred to the piece as: "One of the most moving and memorable assignments of my career."
In the piece, Zelensky and his wife are shown together inside of their compound in Mariinsky Palace on the outskirts of Kyiv.
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In one picture, Zelenska is pictured beside the downed remains of the world's largest plane, the Antonov AN-225. Russian operatives sabotaged the cargo aircraft at an airfield in Kyiv in February.
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Zelenska told Vogue: "These have been the most horrible months of my life, and the lives of every Ukrainian."
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She continued: "Frankly I don't think anyone is aware of how we have managed emotionally. We're looking forward to victory. We have no doubt we will prevail. And this is what keeps us going."
The former comedy writer also said: "I like being backstage—it suited me. Moving into the limelight was quite difficult for me."
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Conservative activist Scott Presler tweeted: "Why did we send $54 billion to Ukraine, so Zelensky & his wife could pose for Vogue? You're at war & you've got time for photo shoots?"
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Texas Congresswoman Mayra Flores tweeted: "Biden: Let's continue to send billions of dollars in foreign aid to Ukraine; they need it!" She continued: "Reality: The Zelensky family graces us with a photo shoot to be on the cover of Vogue magazine."
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There is no proof that suggests any of the $60 billion given to Ukraine by the Biden administration was used to pay for the photo shoot.
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On the different side of the debate, Verizon executive Tami Erwin tweeted support for the piece.
Erwin said: "An outstanding profile. Olena Zelenska has done an incredible job representing her people, ensuring the world knows the story of women and children of Ukraine - and continuing to give voice to the many in need."