Abstract This study incorporated the dual-motivational theory with psychological reactance theory to investigate the cognitive and emotional responses that unfold when audience members encounter a freedom-threatening message and experience psychological reactance. A total of 100 college-aged, daily e-cigarette users were purposively recruited and randomly assigned to view four, 30-second anti-vaping public service announcements (PSAs) in random presentation featuring either dogmatic or suggestive language. As expected, daily e-cigarette users in the dogmatic anti-vaping PSA condition self-reported greater unpleasantness, freedom threat, psychological reactance, and behavioral intentions to use e-cigarettes than daily e-cigarette users in the suggestive anti-vaping PSA condition. Daily e-cigarette users in the dogmatic anti-vaping PSA condition also had greater defensive motivational reactivity during message exposure as indicated by greater corrugator muscle activation, skin conductivity levels, and less heart rate deceleration than daily e-cigarette users in the suggestive anti-vaping PSA condition. Taken together, this study provides substantial evidence of the psychophysiological and defensive nature of psychological reactance theory.