Abstract: Design and preparation of bi–functional oxygen electrocatalysts with low cost, high activity and good stability proves much important for the application of advanced energy storage systems (including fuel cells and metal-air batteries). In this work, home-made defective carbon fibers (CNFs-D)/CoO hybrid electrocatalyst is successfully prepared by a simple impregnated adsorption method followed by pyrolysis process using CNFs-D as carbon precursor. Scanning electron microscope, X-ray diffraction and other techniques are employed to detect the morphology, structure and surface property of the obtained samples. Meanwhile, cyclic voltammetry, linear sweep voltammetry and other methods are used to measure the catalytic performance of the obtained samples. The results show that the as-prepared CNFs-D/CoO hybrid electrocatalyst shows much better bi-functional oxygen catalytic performance when compared to other comparison samples. And this excellent oxygen catalytic performance is mainly due to the fact that CNFs-D possesses larger specific surface area, higher defect degree and stronger interaction with cobalt source. Our adopted preparation strategy offers a good example for the design of transition metal compound/carbon hybrid electrocatalysts.