The deliberate control of facial expressions is an important ability in human interactions, in particular for mothers with prelinguistic infants. Because research on this topic is still scarce, we investigated the control over facial expressions in a Stroop-like paradigm. Mothers of 2-6 months old infants and nullipara women produced smiles and frowns in response to verbal commands written on distractor faces of adults or infants showing expressions of happiness or anger/distress. Analyses of video recordings with a machine classifier for facial expression revealed pronounced effects of congruency between the expressions required by the participants and those displayed by the face stimuli on the onset latencies of the deliberate facial expressions. With adult distractor faces this Stroop effect was similar whether participants smiled or frowned. With infant distractor faces mothers and non-mothers showed indistinguishable Stroop effects on smile responses; however, for frown responses, the Stroop effect in mothers was smaller than in non-mothers. We suggest that for frown responses in mothers when facing infants, the effect of mimicry or stimulus response compatibility, leading to the Stroop effect, is offset by a caregiving response or empathy.