This study investigated the effects of adrenocortical functioning on infant learning during an emotionally challenging event (brief separation from mother). We also explored possible relationships between maternal sensitivity and both infant and maternal cortisol reactivity during the learning/maternal separation episode. Sixty-three 3-month-olds and their mothers were videotaped for a 10 min normal interaction period, and mother-infant behavioral synchrony was measured using Isabella and Belsky's [Isabella, R. A., & Belsky, J. (1991). Interactional synchrony and the origins of infant-mother attachment: A replication study. Child Development, 62, 373-384] coding scheme. The percentage of synchronous behaviors served as a measure of maternal sensitivity. Learning and short-term memory involved relating the infant's mother's voice with a moving colored block in a preferential looking paradigm. Infants whose cortisol increased during the session showed no learning or memory, infants whose cortisol declined appeared to learn and remember the association, while infants whose cortisol did not change evidenced learning, but not memory for the voice/object correspondence. Sensitivity and cortisol reactivity were correlated for mothers, but not for infants. Infant and maternal cortisol values for the first sampling period were highly correlated, but their cortisol reactivity values were uncorrelated, supporting the notion that infants and mothers have coordinated adrenocortical functioning systems when physically together, but become uncoordinated during a separation/learning event.