Schumer posed topless, wearing just heels and underwear in the shot.
The actress posted her photograph, different than Pirelli's usual pinup style photos, to Twitter and Instagram Monday morning with the description, "Beautiful, gross, strong, thin, fat, pretty, ugly, sexy, disgusting, flawless, woman."
"I'm a great admirer of comediennes. The Amy Schumer portrait added some fun," Leibovitz said in a statement. "It's as if she didn't get the memo saying that she could keep her clothes on."
In foreword of the calendar, Yao Chen said the 2016 calendar is breaking new ground.
"On Monday, a new kind of Pirelli calendar was unveiled for 2016, showcasing 12 months of fully clad women (mostly) chosen for their achievements," the foreword read.
"Though the calendar has, on rare occasions, featured women in clothes, this is the first time there is no provocation in the posing, and the first time the attraction of the subjects is in their résumés, not their measurements."
Pirelli shared a behind-the-scenes video that gives viewers a glimpse of the studio shoot. "When Pirelli approached me, they said they wanted to make a departure from the past," Leibovitz said in a statement. "They suggested the idea of photographing distinguished women. After we agreed on that, the goal was to be very straightforward. I wanted the pictures to show the women exactly as they are, with no pretense."
"I felt I looked more beautiful than I've ever felt in my life, and I felt like it looked like me," Schumer said in the video.
"I love that they're embracing the moment that we're in," Ava DuVernay added.
The 2016 edition brings women of power and outstanding accomplishment. In the first few Pirelli Calendars of the 1960s, as well as Peter Lindbergh's 2002, Patrick Demarchelier's 2008 and Steve McCurry's 2013 calendars, there are no nudes.
"The 2000 Calendar was an exercise in photographing nudes. It was a simple concept," Leibovitz said in a statement. "For 2016, we did something completely different, but it is still simple. It is a classic set of black-and-white portraits made in the studio."
Williams showed over her back muscles and athletic physique, posing with only underwear. The other models include accomplished women such as president of Lucas Films Kathleen Kennedy, director Ava Duvernay and singer-songwriter Patti Smith.
The full list of the women in the 2016 edition includes:
Foreward: Yao Chen
January: Natalia Vodianova
February: Kathleen Kennedy
March: Agnes Gund and Sadie Rain Hope-Gund
April: Serena Williams
May: Fran Lebowitz
June: Mellody Hobson
July: Ava Duvernay
August: Tavi Gevinson
September: Shirin Neshat
October: Yoko Ono
November: Patti Smith
December: Amy Schumer
