We focused on job interviews as critical examples of complex social interaction in organizational contexts. We aimed at investigating the effect of face-to-face vs. computer-mediated interaction, of role (candidate, recruiter), and of the interview phase (introductory, attitudinal, technical, conclusive) on intra-brain and inter-brain connectivity measures and autonomic synchronization. Twenty expert recruiters and potential candidates took part in a hyperscanning investigation. Namely, electroencephalography (delta, theta, alpha, beta bands) and autonomic (skin-conductance, heart-rate) data were collected in candidate-recruiter dyads during a simulated job interview and then concurrently analyzed. Analyses highlighted a link between face-to-face condition and greater intra-/inter-brain connectivity indices in delta and theta bands. Furthermore, intra-brain and inter-brain connectivity measures were higher for delta and theta bands in the final interview phases compared to the first ones. Consistently, autonomic synchronization was higher during the final interview phases, specifically in the face-to-face condition. Finally, recruiters showed higher intra-brain connectivity in the delta range over frontal and temporoparietal areas, while candidates showed higher intra-brain connectivity in the theta range over frontal areas. Findings highlight the value of hyperscanning investigations in exploring social attunement in professional contexts and hint at their potential to foster neuroscience-informed practices in human resource management processes.