The development of externalizing behavior in young children is shaped by the complex interaction of temperament, neural mechanisms, and environmental factors. This study explored how child frontal alpha asymmetry (FAA) and child negative affect jointly moderate the relationship between mindful parenting and child externalizing behavior. The sample, drawn from families in the Netherlands, included reports from 128 mothers and 103 partners on mindful parenting, and on children’s negative affect and externalizing behavior. FAA was measured in 95 four-year-old children during an EEG session while they watched an animated video. Results indicated that children with high negative affect and greater left-sided FAA displayed the most externalizing behavior when maternal mindful parenting was low, but the least when mindful parenting was high. In contrast, no significant effects were found for children with lower negative affect or in partner-reported data. These findings suggest that children with both high negative affect and greater left-sided FAA are more sensitive to the quality of mindful parenting, particularly from mothers, aligning with the environmental sensitivity framework. Future research should replicate these findings, ideally in a larger sample, and further examine the long-term, cumulative impact of FAA and negative affect on the development of behavioral problems.