Graphitic carbon nanocapsules (GCNs) with high crystallinity and a large specific surface area (SSA) have been prepared in high yield by a solid‐state pyrolysis route using a polyacrylic weak‐base anion‐exchange resin (PAWBA) as the carbon source. A possible mechanism for the formation of the GCNs is proposed based on a series of experiments, including TG, FTIR, Raman, and TEM analyses, as well as on the structure of PAWBA: The catalytic iron particles are surrounded by the active carbon atoms derived from PAWBA during the pyrolytic process, which then escape from thecarbon nanocapsules as the pyrolytic temperature is further increased to finally yield the GCNs. The synthesized GCNs were used as an excellent support of platinumnanoparticles (3–5 nm) for methanol electro‐oxidation. The Pt/GCN electrocatalyst exhibited a higher catalytic activity and better durability towards methanol electro‐oxidation than Pt/C (Vulcan XC‐72R support) and commercial Pt/C(JM) catalysts. The current density of the Pt/GCN catalyst for methanol electro‐oxidation is as high as 275 A/g Pt, whereas for the Pt/C and Pt/C(JM) catalysts the values are only 190 and 184 A/g Pt, respectively.