The transition to technologically-assisted communication has permeated all facets of human social life; yet, its impact on the social brain is still unknown and the effects may be particularly intense during periods of developmental transitions. Applying a two-brain perspective, the current preregistered study utilized hyperscanning EEG to measure brain-to-brain synchrony in 62 mother-child pairs at the transition to adolescence (child age; M = 12.26, range 10–14) during live face-to-face interaction versus technologically-assisted remote communication. The live interaction elicited 9 significant cross-brain links between densely inter-connected frontal and temporal areas in the beta range [14–30 Hz]. Mother’s right frontal region connected with the child’s right and left frontal, temporal, and central regions, suggesting its regulatory role in organizing the two-brain dynamics. In contrast, the remote interaction elicited only 1 significant cross-brain-cross-hemisphere link, attenuating the robust right-to-right-brain connectivity during live social moments that communicates socio-affective signals. Furthermore, while the level of social behavior was comparable between the two interactions, brain-behavior associations emerged only during the live exchange. Mother-child right temporal-temporal synchrony linked with moments of shared gaze and the degree of child engagement and empathic behavior correlated with right frontal-frontal synchrony. Our findings indicate that human co-presence is underpinned by specific neurobiological processes that should be studied in depth. Much further research is needed to tease apart whether the “Zoom fatigue” experienced during technological communication may stem, in part, from overload on more limited inter-brain connections and to address the potential cost of social technology for brain maturation, particularly among youth.