Maternal body odors serve as important safety-promoting and social recognition signals, but their role in human brain maturation is largely unknown. Utilizing ecological paradigms and dual- electroencephalography recording, we examined the effects of maternal chemosignals on brain-to-brain synchrony during infant-mother and infant-stranger interactions with and without the presence of maternal body odors. Neural connectivity of right-to-right brain theta synchrony emerged across conditions, sensitizing key nodes of the infant’s social brain during its maturational period. Infant-mother interaction elicited greater brain-to-brain synchrony; however, maternal chemosignals attenuated this difference. Infants exhibited more social attention, positive arousal, and safety/approach behaviors in the maternal chemosignals condition, which augmented infant-stranger neural synchrony. Human mothers use interbrain mechanisms to tune the infant’s social brain, and chemosignals may sustain the transfer of infant sociality from the mother-infant bond to life within social groups.