The nature of the association between physical activity and positive affect is complex, prompting experts to recommend continued examination of moderating variables. The main purpose of this 2-week field study was to examine the influence of situational motivational regulations from self-determination theory (SDT) on changes in positive affect from pre-to post-to 3-hours post-physical activity. Another purpose was to clarify the relationship between physical activity intensity [i.e., Ratings of Perceived Exertion (RPE)] and positive affect at the stated time points. This study employed an experience sampling design using electronic questionnaires. Sixty-six healthy and active, multiplerole women provided recurrent assessments of their physical activity, situational motivation, and positive affect in their everyday lives over a 14-day period. Specifically, measures were obtained at the three time points of interest (i.e., pre-, post-, 3-hours post-physical activity). The data were analyzed using multilevel modeling. Results showed that intrinsic motivation was related to post-physical activity positive affect while the influence of identified regulation appeared 3-hours post-physical activity. In addition, RPE, which was significantly predicted by levels of introjection, was more strongly associated with an increase in positive affect postphysical activity than three hours later. The theoretical implications of these findings vis-à vis SDT, namely in regards to a viable motivational sequence predicting the influence of physical activity on affective states, are discussed. The findings regarding the differential influences of RPE and motivational regulations carries applications for facilitating women's well-being.