In the picture, Jenner's face is concealed as she hugs Scott. All she's wearing is a cowboy hat.
She captioned the photo "When Houston meets LA..." adding the Playboy handle and the hash tag #ComingSoon. The Houston/LA line references their hometowns.
Playboy also shared their own pictures from the photo shoot, including a close-up of Jenner's red lips close to the jewelry around Scott's neck.
The photo shoot was for Playboy's upcoming "Pleasure" issue, which, according to Playboy, will be "a celebration of the things that bring us joy: sex, art, food, music, spiritual connection, travel, cannabis and community."
"So hawt," said nisawildaa on Instagram, while another complimented Jenner on her one piece of clothing, saying "nice hat."
The picture has already gotten more than 7 million likes, despite just being posted a couple of hours ago.
Khloe Kardashian was taken aback by the reveal, responding with "Ohhhhhhhhh good morning! .... Shhhooooookkt."
There is no release date yet for the Pleasure issue.