We report the synthesis of a composite from cobalt porphyrin-based metal organic framework (MOF) and multi-walled carbon nanotube (MWCNT), possessing good catalytic activity toward oxygen reduction (OR) and oxygen evolution (OE) processes. A 3-D porous coordination network (PCN) with 3-D nanochannels was synthesized using ultrastable Zr6 clusters and tetrakis(4-carboxyphenyl)porphyrin cobalt(II). Located in the backbone of MOF, cobalt porphyrins as the active centers are easily accessible to the reactants. The composite exhibits smaller overpotentials and higher current for OR and OE reactions compared to the commercial Pt/C catalyst. A proton-coupled electron transfer mechanism has been suggested due to the pH dependence of water oxidation on the electrocatalyst. Furthermore, the stability of the catalyst has been verified by various techniques. Our designed heterogeneous, inexpensive, and stable electrocatalyst is a proper candidate for acidic fuel cells and water splitting devices under near neutral condition without requirement of pyrolysis process.