Although research on the neurobiological foundation of social affiliation has implicated the neuropeptide oxytocin in processes of maternal bonding in mammals, there is little evidence to support such links in humans. Plasma oxytocin and cortisol of 62 pregnant women were sampled during the first trimester, last trimester, and first postpartum month. Oxytocin was assayed using enzyme immunoassay, and free cortisol was calculated. After the infants were born, their interactions with their mothers were observed, and the mothers were interviewed regarding their infant-related thoughts and behaviors. Oxytocin was stable across time, and oxytocin levels at early pregnancy and the postpartum period were related to a clearly defined set of maternal bonding behaviors, including gaze, vocalizations, positive affect, and affectionate touch; to attachment-related thoughts; and to frequent checking of the infant. Across pregnancy and the postpartum period, oxytocin may play a role in the emergence of behaviors and mental representations typical of bonding in the human mother.