We examined associations between mothers' (N = 137; 77.7% White/non-Hispanic) neural responding implicated in facial encoding (N170) and attention (P300) to infant emotional expressions and direct observations of their caregiving behaviors toward their 6-month-old infants. We also explored the moderating role of mother-reported and observer-rated infant temperamental distress. Few direct associations emerged that were not further moderated by temperament. Specifically, a dampened N170 to infant distress (vs. neutral) expressions was associated with mothers' intrusiveness, and a larger P300 to infant happy (vs. neutral) expressions was associated with mothers' sensitivity to distress. Among mothers who perceived their infants as high in temperamental distress, neural responding reflective of distinguishing (N170) and attending (P300) to infant distress (vs. neutral) expressions was associated with maternal sensitivity to distress, and neural responding reflective of encoding (N170) infant emotional (distress, happy, vs. neutral) expressions was associated with greater maternal sensitivity to nondistress. At lower levels of mother-reported temperamental distress, a heightened N170 to infant emotional (distress, happy, vs. neutral) expressions was associated with mothers' detachment. Findings indicate that distinctive patterns of neural responding to infant emotional expressions are associated with specific caregiving behaviors and demonstrate the significance of mothers' perceptions of infant temperamental distress in moderating the extent to which neural responding to infant expressions is associated with their caregiving behaviors. (PsycInfo Database Record (c) 2025 APA, all rights reserved).