Selective relationships and attachments are central to human health and well-being, both in current societies and during the course of evolution. The presence or absence of social bonds has consequences across the lifespan. The neurobiology of attachment is grounded in neuroendocrine substrates that are shared with reproduction and survival. Experimental studies of species, such as sheep or prairie voles, capable of showing selective social behaviors toward offspring or partners, have provided empirical evidence for the role of oxytocin and vasopressin in the formation of selective attachments. Developmental exposure to social experiences and to peptides, including oxytocin and vasopressin, also can “retune” the nervous system, altering thresholds for sociality, emotion regulation, and aggression. Without oxytocin and without the ability to form attachments the human brain as we know it could not exist. Knowledge of the neurobiology of attachment, and especially the role of oxytocin, also has implications for understanding both healthy behavior and treating mental disorders.