Maternal psychological factors, including anxiety, depression, and substance use, may negatively affect parenting. Previous works with mothers have often assessed each of these factors in isolation despite their frequent co‐occurrence. Psychological factors have also been associated with neural processing of facial stimuli, specifically the amplitude (i.e., size) and latency (i.e., timing) of the face‐specific N170 event‐related potential. In the current study, 106 mothers completed measures assessing maternal psychological factors—anxiety, depression, and substance use. A latent profile analysis was used to identify profiles of psychological factors and assess profile associations with the N170 elicited by infant faces and with parental reflective functioning (PRF) as a measure related to caregiving. Two profiles (termed high and low psychological risk) were identified, with the higher risk profile associated with delayed N170 latency responses to infant faces. An exploratory analysis evidenced an indirect effect between the higher psychological risk profile and lower PRF through delayed N170 latency responses to infant faces. Taken together, maternal psychological risk across multiple indicators may together shape neural processing of infant faces, which may have downstream consequences for caregiving.