Maternal sensitivity in response to infant distress is related to a number of physiological processes, including electrocortical activity and activation of the sympathetic nervous system. Several studies have examined these systems in isolation, but limited work to date has investigated how they may moderate one another in relation to maternal behavior. The current exploratory study aimed to investigate the interactive effect of the late positive potential (LPP) and skin conductance level (SCL) on observed maternal sensitivity to distress. Ninety-five mothers of 6- to 12-month-old infants participated in two reactivity tasks measuring their LPP and SCL responses to child crying stimuli. Maternal sensitivity to distress was coded from video-recorded mother–infant interactions. Results showed a significant interaction effect, such that LPP reactivity to infant crying was positively related to maternal sensitivity to distress among mothers with relatively low SCL reactivity. The findings highlight the importance of examining multiple systems when characterizing the physiological basis of maternal behavior.