Motivations for and against sex are salient predictors of engaging in or abstaining from sex in cross-sectional studies. Participants (N = 637, 41.4% male) provided data on their motivations for and against sex and lifetime sexual behavior prior to entering college and six months into the first year in college. Longitudinal data were used to examine differences on motivations for and against sex reported the summer before college entrance for students who continued to abstain (Nevers, 44.7%), transitioned to sexual behavior in the following months (Transitioners, 11.0%), and who were previously sexually active (Actives, 44.3%). Multivariate analysis of variance analyses indicated that Transitioners evidenced mean-level differences in motivations surrounding sex (greater intimacy and enhancement motives for sex, lower values motives against sex) prior to their behavioral initiation compared to Nevers. In addition, Transitioners reported greater changes in motivations from pre-college to the six-month follow-up, including increased enhancement motivations for sex and decreased values and not ready motivations against sex. Men reported more important motivations for sex and less important motivations against sex than women, with an interaction showing that sexually experienced women reported more important intimacy motivations and sexually inexperienced men reported more important coping motivations for sex. Identifying salient motivations associated with imminent changes in sexual behavior may support the development of sexual health promotion programs that seek to reach sexually inexperienced individuals at important times of transition.