Microstates represent brief periods of quasi-stable electroencephalography (EEG) scalp topography, offering insights into dynamic fluctuations in event-related potential (ERP) topographies. Despite this, there is a lack of a comprehensive systematic overview of microstate findings concerning cognitive face processing. This review aims to summarize ERP findings on face processing using microstate analyses and assess their effectiveness in characterizing face-related neural representations. A literature search was conducted for microstate ERP studies involving healthy individuals and psychiatric populations, utilizing PubMed, Google Scholar, Web of Science, PsychInfo, and Scopus databases. Twenty-two studies were identified, primarily focusing on healthy individuals (n = 16), with a smaller subset examining psychiatric populations (n = 6). The evidence reviewed in this study suggests that various microstates are consistently associated with distinct ERP stages involved in face processing, encompassing the processing of basic visual facial features to more complex functions such as analytical processing, facial recognition, and semantic representations. Furthermore, these studies shed light on atypical attentional neural mechanisms in Autism Spectrum Disorder (ASD), facial recognition deficits among emotional dysregulation disorders, and encoding and semantic dysfunctions in Post-Traumatic Stress Disorder (PTSD). In conclusion, this review underscores the practical utility of ERP microstate analyses in investigating face processing. Methodologies have evolved towards greater automation and data-driven approaches over time. Future research should aim to forecast clinical outcomes and conduct validation studies to directly demonstrate the efficacy of such analyses in inverse space.