We report a facile St?ber approach to prepare polyphenol-based resin polymer spheres using tannic acid and formaldehyde as reactants. The tannic acid-formaldehyde (TAF) spheres directly convert into carbon spheres with monodispersity and structural integrity. In addition, TAF-Fe complex spheres are carbonized into Fe nanoparticles (NPs) decorated carbon spheres (TAF-C@Fe), which are successfully applied as electrocatalysts for oxygen reduction reaction (ORR) in alkaline media. The electrocatalyst exhibits similar catalytic activity but better methanol tolerance performance to 20% commercial Pt/C in alkaline media. This feasible strategy presents a novel precursor for fabricating and tailoring the structure, composition, and size of polyphenol resin and derived carbon-based materials for energy conversion and storage.