Prior research suggests that the construct of emotional instability may be salient to bulimia nervosa (BN), but no study to date has used ecological momentary assessment (EMA) to examine its temporal association with binge eating and purging. In the current study, 133 women with DSM-IV BN used portable digital devices to provide multiple daily negative affect (NA) and positive affect (PA) ratings and record eating disorder behaviors over 2 weeks. Two state-of-the art indices quantified affective instability: probability of acute change (PAC), which represents the likelihood of extreme affective increases, and mean squared successive difference (MSSD), which represents average change over successive recordings. For extreme affective change, results revealed that on bulimic behavior days, extreme NA increases were less likely after bulimic behaviors than before them, and extreme increases in PA were more likely after bulimic behaviors than during the same time period on non-bulimic behavior days. However, average NA instability (i.e., MSSD) was (a) greater on bulimic behavior days than non-bulimic behavior days, (b) greater after bulimic behaviors than during the same time period on non-bulimic behavior days, and (c) greater after bulimic behaviors than before them. Results lend support to the notion that bulimic behaviors are negatively reinforcing (i.e., via post-behavior acute affective changes), but also indicate that these behaviors may exacerbate overall affective dysregulation. These findings may improve understanding of BN maintenance and inform the development of novel interventions or refinement of existing treatments.