The in situ free carbon generated in polymer-derived ceramics (PDCs) plays a crucial role in their unique microstructure and resultant properties. This study advances a new phenomenon of graphitization of PDCs. Specifically, whether in micro-/nanoscale films or millimeter-scale bulks, the surface/interface radically changes the fate of carbon and the evolution of PDC nanodomains, promotes the graphitization of carbon, and evolves a free carbon enriched layer in the near-surface/interface region. Affected by the enrichment behavior of free carbon in the near-surface/interface region, PDCs exhibit highly abnormal properties such as the skin behavior and edge effect of the current. The current intensity in the near-surface/interface region of PDCs is orders of magnitude higher than that in its interior. Ultrahigh conductivity of up to 14.47Scm-1 is obtained under the action of the interface and surface, which is 5-8 orders of magnitude higher than that of the bulk prepared under the same conditions. Such surface/interface interactions are of interest for the regulation of free carbon and its resultant properties, which are the core of PDC applications. Finally, the first PDC thin-film strain gauge that can survive a butane flame with a high temperature of up to ≈1300°C is fabricated.