Objective: Given the growing popularity of ayahuasca and other hallucinogens, we sought to identify related expectancies and their role in why people might use this psychoactive brew rather than classic hallucinogens like LSD or psilocybin. Method: Experienced users (N 5 139) completed an online survey about their use of hallucinogens (including ayahuasca), how their ayahuasca experiences differed from those with other hallucinogens, as well as their intentions to use hallucinogens (including ayahuasca) in the future. Results: Participants expected ayahuasca effects to differ meaningfully from the effects of other hallucinogens in multiple domains. Expected differences involved positive connections to nature (and other people), dramatic (or terrifying) thoughts, high variability of effects, and physical reactions. Intentions to use ayahuasca in the future increased as expectancies for positive connections increased, but decreased as physical reactions increased. One version of the full Novelty of Ayahuasca scale significantly covaried with the likelihood of using ayahuasca over other hallucinogens in the future, while another version did not. This result calls for further work examining how users perceive certain ayahuasca-induced effects. Conclusions: These findings reveal that expectancies for ayahuasca differ from those for other hallucinogens, and impact an individual’s willingness to try the substance again. Understanding these differences might help those who are interested in the therapeutic potential of hallucinogens decide among those available. Future studies might examine how these expectancies predict intentions to use ayahuasca (and other hallucinogens) longitudinally. Comparable approaches could also identify unique expectancies for other hallucinogens to see if those predict a preference for one over others.