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Social learning theories suggest that outcome expectancies are strong determinants of behavior, and studies find that alcohol and cannabis expectancies are associated with negative substance use outcomes. However, there are no measures to date that assess expectancies for simultaneous alcohol and cannabis use (SAM), often referred to as SAM, despite strong links with negative consequences and rising time trends. The present study sought to provide initial validation of test scores for the Anticipated Effects of Simultaneous Alcohol and Cannabis Use Scale (AE-SAM), using a sample of past month college student simultaneous users (N = 434). Exploratory factor analysis and confirmatory factor analysis conducted in random half samples suggested five expectancy factors, representing high arousal positive, high arousal negative (alcohol driven), high arousal negative (cannabis driven), low arousal positive, and low arousal negative expectancies. The factor structure was invariant across sex, race/ethnicity, and simultaneous use frequency, and demonstrated convergent and discriminant validity with other alcohol/cannabis expectancy measures. AE-SAM high arousal positive expectancies were associated with simultaneous use frequency and heavier drinking/cannabis use, AE-SAM high arousal negative (cannabis driven) expectancies were associated with less frequent simultaneous use and more negative alcohol consequences, and AE-SAM low arousal negative expectancies were associated with less cannabis use. Effects of AE-SAM high arousal positive and high arousal negative (cannabis driven) expectancies remained, above and beyond other expectancy measures, suggesting that AE-SAM expectancies provide additional information beyond single substance expectancies. The results demonstrate the feasibility and utility of assessing simultaneous use expectancies, and lay groundwork for future research on simultaneous use expectancies in relation to alcohol and cannabis couse outcomes. Public Significance Statement: The present study provided initial development and validation of test scores for a five-factor simultaneous alcohol and cannabis expectancies measure that spanned the full range of valence (positive vs. negative) by arousal (high arousal vs. low arousal) affective space. Simultaneous use expectancies were incrementally associated with use behavior and negative substance use outcomes and should be considered in ongoing prevention efforts related to alcohol, cannabis, and couse across the lifespan. [ABSTRACT FROM AUTHOR]