Jenner, 65, one-time Olympic gold medalist, poses on the cover in a one-piece outfit.
In the interview, Jenner said she felt as Bruce she was lying to the world and this cover shoot will change everything, reported Vanity Fair.
"As soon as the Vanity Fair cover comes out, I'm free. Bruce always had to tell a lie. Every day he always had a secret from morning till night. Caitlyn doesn't have any secrets," she said.
"How beautiful! Be happy, be proud, live life YOUR way!," tweeted step-daughter Kim Kardashian.
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"Now that's a cover. Be free now pretty bird." tweeted Kendall Jenner.
Jenner also launched a new Twitter account as @Caitlyn_Jenner which garnered her 1 million followers within hours.
"I'm so happy after such a long struggle to be living my true self. Welcome to the world Caitlyn," she wrote.