She appears in the episode "Rattlesnake" where she tells Stinky the Skunk and Jake the Polar Bear all about rattlesnakes in the first half and then other snakes in the second half. Stinky even wondered if he can swallow someone like Jake. By the end of the episode, it appeared that Kiki had swallowed Jake only for Jake to appear. It turned out that Kiki actually at all of Armstrong the Chicken Hawk's Chawky Hawkies.
Before her appearance in this episode, Kiki the Rattlesnake appeared in the episode "Mouse" where she alongside Timothy the Owl and Virginia the Red Fox try to eat Stanley the Mouse. During that time, Kiki was performed by Katherine Smee.
She is a recycled version of Victor the Rattlesnake.