The evolution of humans as a highly social species tuned the brain to the social world; yet the mechanisms by which humans coordinate their brain response online during social interactions remain unclear. Using hyperscanning EEG recordings, we measured brain-to-brain synchrony in 104 adults during a male-female naturalistic social interaction, comparing romantic couples and strangers. Neural synchrony was found for couples, but not for strangers, localized to temporal-parietal structures and expressed in gamma rhythms. Brain coordination was not found during a three-minute rest, pinpointing neural synchrony to social interactions among affiliative partners. Brain-to-brain synchrony was linked with behavioral synchrony. Among couples, neural synchrony was anchored in moments of social gaze and positive affect, whereas among strangers, longer durations of social gaze and positive affect correlated with greater neural synchrony. Brain-to-brain synchrony was unrelated to episodes of speech/no-speech or general content of conversation. Our findings link brain-to-brain synchrony to the degree of social connectedness among interacting partners, ground neural synchrony in key nonverbal social behaviors, and highlight the role of human attachment in providing a template for two-brain coordination.