Researchers have identified a strong link between sexual compulsivity (SC) and risky sexual behavior among men who have sex with men (MSM). Meanwhile, affect/mood has also been connected with negative sexual health outcomes (sexually transmitted infection/human immunodeficiency virus [HIV] transmission, sexual risk, sex under the influence of drugs/alcohol). Given that SC is characterized by marked distress around one's own sexual behavior, affect may play a central role in SC and HIV risk behavior. Data were taken from the Pillow Talk Project, a pilot study conducted in 2008-2009 with 50 highly sexually active MSM (9 or more male sex partners, ≤ 90 days), of which half displayed SC symptoms and half did not. Forty-seven men completed a daily diary online for 30 days (n = 1,060 diary days), reporting on their sexual behavior and concurrent affect: positive activation, negative activation, anxious arousal, and sexual activation. We conducted HLM analyses using daily affect (Level 1, within subjects) and SC and HIV status (Level 2, between subjects) to predict sexual behavior outcomes. Increased negative activation (characterized by fear, sadness, anger, and disgust) was associated with reduced sexual risk behavior, but less so among sexually compulsive MSM. Sexual activation was associated with increased sexual risk taking, but less so among sexually compulsive MSM. Anxious arousal was associated with increased sexual behavior, but not necessarily sexual risk taking. Findings indicate that affect plays key roles in sexual behavior and sexual risk taking; however, the association between affect and behavior may be different for sexually compulsive and non-sexually compulsive MSM.