Social interactions require both the rapid processing of multifaceted socio-affective signals (e.g., eye gaze, facial expressions, gestures) and their integration with evaluations, social knowledge, and expectations. Researchers interested in understanding complex social cognition and behavior face a “black box” problem: What are the underlying mental processes rapidly occurring between perception and action and why are there such vast individual differences? In this review, we promote electroencephalography (EEG) microstates as a powerful tool for both examining socio-affective states (e.g., processing whether someone is in need in a given situation) and identifying the sources of heterogeneity in socio-affective traits (e.g., general willingness to help others). EEG microstates are identified by analyzing scalp field maps (i.e., the distribution of the electrical field on the scalp) over time. This data-driven, reference-independent approach allows for identifying, timing, sequencing, and quantifying the activation of large-scale brain networks relevant to our socio-affective mind. In light of these benefits, EEG microstates should become an indispensable part of the methodological toolkit of laboratories working in the field of social and affective neuroscience.