Abstract: Carbon nanofiber(CNF) with different microstructures were prepared via catalytic chemical vapor deposition method using different catalysts.The microstructures and textural properties of CNF were characterized by high resolution transmission electron microscope and cryogenic N_2 physisorption method.The cyclic voltammetry analysis was used to study the oxygen reduction reaction(ORR) activity of CNF electrodes with different microstructures.Graphite was used as a reference for comparison.It was found that the CNF has a high catalytic activity for ORR in spite of the microstructures of CNF,and high capacitance compared with the graphite.The impact of microstructures of CNF on their electrochemical performance is evident,probably resulting from the different specific surface area and surficial chemical property of CNF.