Psychological pain is a prominent symptom in people who experience depression, but its relation with physiological measures has not been explored. This study compared two measures of psychological pain, the Orbach & Mikulincer Mental Pain (OMMP) questionnaire and the Psychache Scale, for their relationship with resting-state heart rate variability (HRV) in 35 adults with a history of depression. Low-frequency HRV decreased significantly with increasing psychological pain, particularly in participants who did not use antidepressants, while the beat-to-beat fractal dimension decreased in participants who did use antidepressants. Neither heart rate nor high-frequency HRV was associated with psychological pain. These results suggest a state of arousal characterized by increased sympathetic activity. Results also indicate that the OMMP may be a more accurate measure of autonomic arousal associated with current psychological pain than the Psychache Scale.