Biomass-derived cobalt-coordinated N-doped carbon (CoNC) for C–H bond oxidation is synthesized by a facile procedure based on pyrolysis of cobaltporphyrin with natural, amino acid-rich biomass casein as a supplementary nitrogen source. The catalysts are characterized by techniques such as transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The obtained CoNC catalyst has a high metal content and dispersion and shows superior catalytic performance in C–H bond oxidation with molecular oxygen as oxidant under solvent-free conditions. This is attributed to the promotion of the Co–N_x moiety originating from cobaltporphyrin. Moreover, the catalyst shows remarkable stability and can be recycled several times without losing its activity.