The Keeping Up with the Kardashians star is seen donning a white bustier with long brown locks and simple makeup in the photo taken by renowned photographer Annie Leibovitz.
And in true Kardashian-Jenner fashion, Caitlyn dons several high-fashion frocks for the photo shoot, including clothes by designers Zac Posen, Badgley Mischka, Halston Heritage, Donna Karan, Herve Leger and Agent Provocateur.
Buzz Bissinger, the Pulitzer Prize–winning contributing editor and author ofFriday Night Lights, spoke with the former Olympian about transitioning to life as a woman.
"If I was lying on my deathbed and I had kept this secret and never ever did anything about it, I would be lying there saying, 'You just blew your entire life,'" Jenner said.
See Bruce Jenner Through the Years:
In a behind-the-scenes look at the Vanity Fair photo shoot, the 65-year-old reality star also talks about time spent training for the decathlon in the 1976 Olympics and how it was a way of avoiding what she was really feeling.
"I was probably at the Games because I was running away from a lot of things," Jenner admitted. "Very very proud of the accomplishment -- I don't want to diminish that accomplishment."
Jenner added that Caitlyn's cover is another huge accomplishment. "The last few days of doing this shoot was about my life, and who I am as a person," she said. "It's not about the fanfare, it's not about people cheering in the stadium, it's not about going down the street and everybody giving you, atta boy, Bruce, pat on the back. This is about your life."
"Bruce always had to tell a lie. He was always living that lie. Every day he always had a secret, from morning to night," Jenner confessed. "Caitlyn doesn't have any secrets. As soon as the Vanity Fair cover comes out, I'm free."
Along with the release of the Vanity Fair story, Caitlyn also started a Twitter account, @Caitlyn_Jenner. "I'm so happy after such a long struggle to be living my true self," the first tweet read on Monday. "Welcome to the world Caitlyn. Can't wait for you to get to know her/me."
I'm so happy after such a long struggle to be living my true self. Welcome to the world Caitlyn. Can't wait for you to get to know her/me.
— Caitlyn Jenner (@Caitlyn_Jenner) June 1, 2015
Jenner's step-daughter Khloe Kardashian was one of the first to throw her support behind the VF cover, Instagramming: "We were given this life because you were strong enough to live it! I couldn't be prouder!!! Caitlyn, You are beautiful!!!"
A video posted by Kendall Jenner (@kendalljenner) on Jun 1, 2015 at 9:57am PDT
Jenner's 19-year-old model daughter Kendall Jenner alsoposted: "Now that's a cover."
Katy Perry, a famous friend of the Kardashian-Jenner family, lovingly tweeted: "Caitlyn is a firework!"