Objective: Sedentary behavior is a health risk but little is known about the motivational processes that regulate daily sedentary behavior. This study was designed to test a dual-process model of daily sedentary behavior, with an emphasis on the role of intentions and habits in regulating daily sedentary behavior. Method: College students (N=128) self-reported on their habit strength for sitting and completed a 14-day ecological momentary assessment study that combined daily diaries for reporting motivation and behavior with ambulatory monitoring of sedentary behavior using accelerometers. Results: Less than half of the variance in daily sedentary behavior was attributable to between-person differences. People with stronger sedentary habits reported more sedentary behavior on average. People whose intentions for limiting sedentary behavior were stronger, on average, exhibited less self-reported sedentary behavior (and marginally less monitored sedentary behavior). Daily deviations in those intentions were negatively associated with changes in daily sedentary behavior (i.e., stronger than usual intentions to limit sedentary behavior were associated with reduced sedentary behavior). Sedentary behavior also varied within people as a function of concurrent physical activity, the day of week, and the day in the sequence of the monitoring period. Conclusions: Sedentary behavior was regulated by both automatic and controlled motivational processes. Interventions should target both of these motivational processes to facilitate and maintain behavior change. Links between sedentary behavior and daily deviations in intentions also indicate the need for ongoing efforts to support controlled motivational processes on a daily basis.