According to the acquired preparedness model, personality traits, such as impulsivity, may influence the learning process, contributing to heightened expectations surrounding risky behaviors (i.e., alcohol use, sexual risk-taking). As bisexual women demonstrate heightened risk for hazardous alcohol- and sex-related behaviors, the present study examined a sequential pathway, whereby the relation between impulsivity and sexual risk-taking is mediated through sex-related alcohol expectancies and alcohol use. Data were collected from 225 self-identified cisgender, bisexual women between the ages of 18 and 30 years (M = 22.77, SD = 3.45), who participated in an online survey. Participants reported on impulsivity, sex-related alcohol expectancies, alcohol use, and experiences of sexual risk-taking. Results revealed that sex-related alcohol expectancies and alcohol use sequentially mediated the relation between impulsivity and sexual risk-taking. Thus, greater impulsivity was related to greater sexual risk-taking through heightened sex-related alcohol expectancies and elevated alcohol use. Findings from this study highlight mechanisms associated with risky drinking and sexual behaviors among this at-risk population. Such information could aid the development of more efficacious prevention and intervention programs aimed at reducing consequences associated with alcohol use and sexual risk-taking among bisexual women. Bisexual women are at heightened risk for alcohol-related problems, including sexual risk-taking. Findings from the current study identify impulsivity and sex-related alcohol expectancies as independent and integrative predictors of such risky behaviors. Incorporation of these constructs may aid in the development of more efficacious clinical methods aimed at bettering health outcomes among bisexual women.