Binuclear ball‐type metallophthalocyanines, Co2Pc2(EP)4, were wrapped on porous carbon Z67‐900 materials using a facilely “π–π assembly” method to prepare Co2Pc2(EP)4@Z67‐900 catalysts for oxygen reduction reactions (ORR). The XRD and pore size distribution results indicate that the presence of high graphitization degree and porosity distribution in Z67‐900. The high graphitization degree of Z67‐900 carbon materials is beneficial for the formation of π–π interaction based on the π electron‐conjugated structure of the binuclear ball‐type metallophthalocyanines Co2Pc2(EP)4 system. The electrocatalytic test shows that the reduction potential −0.18 V (vs. SCE) for Co2Pc2(EP)4@Z67‐900 is 20% higher than that of commercial Pt/C. The porosity distribution in Z67‐900 promotes the oxygen molecules concentration around the active sites MN4‐type Co2Pc2(EP)4 macrocyclic system to form an intermediate O2ads‐Co2Pc2(EP)4@Z67‐900. The π–π interactions between Co2Pc2(EP)4 and Z67‐900 decreased the activation energy of the *OOH dissociation step in a four‐electron ORR process. It provides a theoretical basis for the subsequent application research of zinc‐air batteries.