Emotions play a critical role in health risk behaviors, including substance use. However, current research often focuses exclusively on average levels of positive and negative affect, neglecting the complexity of daily emotional patterns. By capturing multiple dimensions of affect, including arousal and discrete states, we can improve our understanding of proximal predictors of substance use. The present study demonstrates the utility of a novel methodological approach for assessing affect patterns in daily life in relation to alcohol and cannabis use. Daily diary data from N = 154 young adults who reported recent heavy episodic drinking and simultaneous use of alcohol and cannabis were analyzed using a mixed-indicator latent profile analysis to identify and describe day-level affective patterns and outcomes. Results revealed five distinct day-level profiles of affect: undifferentiated negative affect days, undifferentiated positive affect days, high-arousal positive affect days, mixed affect days, and low reactivity days. Undifferentiated positive affect days, high-arousal positive affect days, and low reactivity days were associated with significantly greater odds of same-day alcohol use compared to days characterized by undifferentiated negative affect (χ² = 10.55, p = .032). Findings suggest that daily affect patterns differentially impact alcohol use and can inform the development of interventions for problematic substance use. Additionally, the innovative methodological approach employed herein could be applicable for investigating the role of emotion in other health behaviors. (PsycInfo Database Record (c) 2024 APA, all rights reserved).