Research attempting to elucidate physical activity (PA) intention-behavior relations has focused on differences in long-term behavior forecasting between people. However, regular PA requires a repeated performance on a daily or within-daily basis. An empirical case study application is presented using intensive longitudinal data from a study of PA in adults to (a) describe the extent to which short-term intention-behavior coupling occurs and (b) explore time-varying predictors of intention formation and short-term intention-behavior coupling. Adults (n = 116) participated in three 4-day waves of ecological momentary assessment (EMA). Each day, participants received EMA questionnaires assessing short-term PA intentions and wore accelerometers to assess whether they engaged in ≥10 min of moderate-to-vigorous physical activity (MVPA) in the 3-hour period after each EMA prompt. Concurrent affective states and contexts were also assessed through EMA. Participants reported having short-term intentions to engage in PA in 41% of EMA prompts. However, participants only engaged in ≥10 min of MVPA following 16% of the prompts that short-term PA intentions were reported indicating an intention-behavior gap of 84%. Odds of intentions followed by PA were greater on occasions when individuals reported higher levels of positive affect than was typical for them. This study is the first to take an EMA approach to describe short-term intention-behavior coupling in adults. Results suggest that adults have difficulty translating intentions into behavior at the momentary level, more so than over longer timescales, and that positive affect may be a key to successfully translating intentions into behavior.