Fentanyl is approved for transmucosal use in the United States as a preanesthetic agent in human pediatric patients and in adults for breakthrough cancer pain. Using this formulation in three species of great ape, including eight orangutans (Pongo pygmaeus), nine chimpanzees (Pan troglodytes), and two gorillas (Gorilla gorilla), fentanyl was offered transmucosally at an intended dose of 10–15 μg/kg based on estimated body weight. The animals were trained to accept and suck slowly on a piece of placebo candy, given as a treat, after an overnight fast. On the day of the study, the animals were given the lollipop formulation of fentanyl. The resulting plasma concentrations of fentanyl supported transmucosal absorption, similar to that reported in humans. This study provides an alternative sedative regimen and yielded half-life data of transmucosal fentanyl in great apes. Although transmucosal fentanyl was a useful adjunct for sedating orangutans and gorillas, its acceptance by chimpanzees before chemical immobilization was suboptimal and unpredictable.