This study examined the links between mothers' frontal EEG asymmetry at rest and during videos of their 5- to 8-month-old infants expressing three emotion states (joy, anger/distress, and neutral interest), mother-infant emotional availability (EA) in the home, mothers' depressive and anxious symptoms, and mothers' emotional experience in response to infant emotion cues. Greater relative right frontal activity at rest was associated with greater maternal anxiety, but was unrelated to EA or mother-reported emotional experience in response to infant emotion cues. A shift toward greater relative right frontal activation in response to infant emotional stimuli was associated with lower maternal anxiety, greater mother-infant EA, and mothers' experience of sadness, concern, irritability, and the absence of joy in response to seeing their own infant in distress. These findings suggest that mothers' in the moment empathetic responding to their infant's emotions, indexed by a shift in frontal EEG asymmetry in response to infant emotional displays, is related to mother-infant EA in the home. Implications for conceptualizing parenting risk are discussed.