Mother–child shared play provides rich opportunities for mutual symmetrical interactions that serve to foster bond formation in dyads. Mutual gaze, a symmetrical behaviour that occurs during direct eye contact between two partners, conveys important cues of social engagement, affect and attention. However, it is not known whether the prefrontal cortical areas responsible for higher-order social cognition of mothers and children likewise exhibit neural symmetry; that is, similarity in direction of neural activation in mothers and children. This study used functional Near-infrared Spectroscopy (fNIRS) hyperscanning on 22 pairs of mothers and their preschool-aged children as they engaged in a 10-min free-play session together. The play interaction was video recorded and instances of mutual gaze were coded for after the experiment. Multivariate linear regression analyses revealed that neural asymmetry occurred during mother–child mutual gaze, where mothers showed a deactivation of prefrontal activity whereas children showed an activation instead. Findings suggest that mothers and children may employ divergent prefrontal mechanisms when engaged in symmetrical behaviours such as mutual gaze. Future studies could ascertain whether the asymmetric nature of a parent–child relationship, or potential neurodevelopmental differences in social processing between adults and children, significantly contribute to this observation.