["Journal of Traumatic Stress, EarlyView. ", "\nAbstract\nNegative self‐evaluative emotions (NSEs), specifically shame and guilt, are notable predictors of the development and maintenance of posttraumatic stress disorder (PTSD) and its most devastating outcomes (e.g., suicide). Yet, there is minimal research examining the real‐time affective and physiological experience of NSEs, like shame, among veterans with PTSD symptoms. This study examined 50 veterans with probable PTSD during shame induction, measuring baseline trait NSEs and PTSD symptoms. Emotions were assessed before and after each task to explore the affective and physiological characteristics of shame and their links to trait NSEs and PTSD. The secondary aim was to compare the effects of induction type on outcomes. Across induction types, NSEs increased during shame induction and decreased after induction at higher levels than non‐NSEs, ηp2 = .472–589. However, only overall autonomic nervous system (heart rate) activity demonstrated this same pattern, ηp2 = .456, as both parasympathetic nervous system (PNS; respiratory sinus arrhythmia), ηp2 = .103, and sympathetic nervous system (SNS; skin conductance level), ηp2  = .345, activity demonstrated significant withdrawal (PNS) and augmentation (SNS) with no natural recovery. Additionally, PTSD symptoms were positively associated with real‐time NSEs, rs = .33–.43, whereas trait guilt was negatively associated with PNS activity, r = −.36. Finally, imaginal shame induction yielded higher NSE reactivity, ηp2 = .039–076, and PNS withdrawal, ηp2 = .046, thus demonstrating the difficulty veterans with PTSD symptoms have recovering from moments of shame, as well as the importance of induction type on eliciting physiological and affective reactivity.\n"]