•Prenatal maternal attention bias to unfamiliar infant face distractors is related to the quality of parenting.•Behavioral and neural processing of unfamiliar infant faces during pregnancy predicts maternal sensitivity to their own infant.•Greater neural decoding of sad vs. happy infant faces predicts greater maternal sensitivity.•Maternal attention bias to and the perceived salience of unfamiliar infant faces operate independently of caregiving experience. While research has shown that attention bias to infant faces is linked to parenting, this work is largely cross–sectional and limited to the postpartum period. Because the transition to motherhood from pregnancy to birth constitutes a sensitive period in cortical reorganization linked to the quality of mother–infant interactions, evaluating attention processes in the maternal cortex prior to the experience of mother-infant face-to-face interactions is critical. To assess behavioural attention and neural responses to infant faces in pregnant mothers, behavioral and electrocortical indices were collected using a Go/No Go task, in which infant and adult faces served as distractors. Results showed that heightened processing of infant faces relative to adult faces (behavioral and electrocortical indices) was related to observations of greater maternal sensitivity. These findings show that prenatal maternal attention bias to and the perceived salience of infant faces serves as an individual cognitive hallmark of maternal sensitivity that acts independently of caregiving experience.