Herein, we report a new approach for the synthesis of non-precious metal electrocatalysts (NPMEs) relying on ionic self-assembly of oppositely charged iron (III) and cobalt (III) porphyirn on carbon in combination with subsequent pyrolysis, leading to carbonized porphyrins uniformly dispersed on carbon without any noticeable agglomerations at nanoscale. As evidenced by thermogravimetric analysis (TGA), the self-assembled porphyrins show a much better thermal stability than each constituent porphyrin, thus possibly preventing the formation of agglomerations that frequently occurred during a pyrolysis process. Additionally, the strong interaction between self-assembled porphyrins and carbon support should also be responsible for the even distribution of carbonized porphyrins according to Fourier transformation infrared (FTIR) spectra. Compared with mechanically mixed and then heat-treated porphyrins, self-assembled and then pyrolyzed porphyrins exhibit a much higher activity toward oxygen reduction reaction (ORR) in both acidic and alkaline medium likely due to well exposed active sites without any aggregation, which has not been achieved prior to this study.