Face perception arises from a collective activation of brain regions in the occipital, parietal and temporal cortices. Despite the wide acknowledgment that these regions act in an intertwined network, the network behavior itself is poorly understood. Here we present a study in which time‐varying connectivity estimated from EEG activity elicited by facial expressions presentation was characterized using graph‐theoretical measures of node centrality and global network topology. Results revealed that face perception results from a dynamic reshaping of the network architecture, characterized by the emergence of hubs located in the occipital and temporal regions of the scalp. The importance of these nodes can be observed from the early stages of visual processing and reaches a climax in the same time‐window in which the face‐sensitive N170 is observed. Furthermore, using Granger causality, we found that the time‐evolving centrality of these nodes is associated with ERP amplitude, providing a direct link between the network state and local neural response. Additionally, investigating global network topology by means of small‐worldness and modularity, we found that face processing requires a functional network with a strong small‐world organization that maximizes integration, at the cost of segregated subdivisions. Interestingly, we found that this architecture is not static, but instead, it is implemented by the network from stimulus onset to ~200 ms. Altogether, this study reveals the event‐related changes underlying face processing at the network level, suggesting that a distributed processing mechanism operates through dynamically weighting the contribution of the cortical regions involved.