Abstract: Metalloporphyrins containing different substitute groups (methyl, methoxy) on the base of phenyl and different metals (Zn，Fe，Co) were synthesized and characterized by EA, UV/vis and ¹H NMR.Effects of different substitute groups and metal ions showed above on the electrochemical behavior of redox were studied by means of the cyclic voltammograms method(CV)in the DMSO solution with TBAP as supporting electrolyte. Furthermore, catalyzed oxygen reduction behavior of cobalt tetramethoxyphenylporphyrin (CoTMPP) based catalysts by CV in 0.5 mol•L^-1 H₂SO₄ was investigated.