Two peripheral functionalized clamp-shaped cobalt porphyrin(2.1.2.1) complexes were synthesized, and their electrocatalytic ORR abilities were investigated. The crystal data and optical and redox properties of them were revised by peripheral modification. The ORR capacities and DFT calculations of F5PhCo and F5NCo suggest superior selectivity for the 4e- ORR pathway. This work further confirms the clamp-shaped cobalt porphyrin complexes are ideal Co-N4 ORR catalysts.