This study investigated maternal oxytocin, caregiving sensitivity and mother-to-infant bonding at 3-months postpartum as predictors of child behavior and psychological outcomes in the preschool years, when controlling for concurrent maternal negative emotional symptoms and adult attachment state-of-mind. Forty-five mother–child dyads were assessed at 3-months and 3.5 years postpartum using mix of questionnaires, observational, interview and biological methods. Results showed that lower levels of maternal baseline oxytocin at 3-months postpartum significantly predicted emotional reactivity in the child at 3.5 years. When maternal adult attachment state-of-mind and negative emotional symptoms were included, lower levels of maternal baseline oxytocin at 3-months postpartum significantly predicted withdrawn child behavior. In addition, unresolved adult attachment and maternal negative emotional symptoms were significantly associated child behavioral disturbance in a range of areas. Findings highlight maternal postnatal oxytocin as a potential indicator of children who may be more likely to show emotional reactivity and withdrawn behavior in the preschool years.