Face processing is a spatiotemporal dynamic process involving widely distributed and closely connected brain regions. Although previous studies have examined the topological differences in brain networks between face and non-face processing, the time-varying patterns at different processing stages have not been fully characterized. In this study, dynamic brain networks were used to explore the mechanism of face processing in human brain. We constructed a set of brain networks based on consecutive short EEG segments recorded during face and non-face (ketch) processing respectively, and analyzed the topological characteristic of these brain networks by graph theory. We found that the topological differences of the backbone of original brain networks (the minimum spanning tree, MST) between face and ketch processing changed dynamically. Specifically, during face processing, the MST was more line-like over alpha band in 0–100 ms time window after stimuli onset, and more star-like over theta and alpha bands in 100–200 and 200–300 ms time windows. The results indicated that the brain network was more efficient for information transfer and exchange during face processing compared with non-face processing. In the MST, the nodes with significant differences of betweenness centrality and degree were mainly located in the left frontal area and ventral visual pathway, which were involved in the face-related regions. In addition, the special MST patterns can discriminate between face and ketch processing by an accuracy of 93.39%. Our results suggested that special MST structures of dynamic brain networks reflected the potential mechanism of face processing in human brain.