Three-dimensional hierarchical Co3O4 microstructures decorated with Ag and Cu oxides were prepared via displacement reaction and subsequent annealing treatment. Photocatalytic properties measurements revealed that the photocatalystic activities of CuO/Co3O4 composites (Co3O4 microstructures decorated with CuO) were enhanced while those of Ag2O/Co3O4 composites (Co3O4 microstructures decorated with Ag2O) were reduced, when compared with those of pure hierarchical Co3O4 microstructures toward the degradation of methyl orange. In addition, CuO/Co3O4 composites exhibited an excellent recyclability ability of photodegradation. The electrochemical properties test indicated that both of the composite oxide electrodes exhibited excellent pseudo-capacitive performance with relatively high specific capacitance and good long-term cycling stability. With the increase of the loaded Ag2O and CuO dosages deposited on the Co3O4 microstructures surface, the specific capacitance values of the composites were increased. Ag2O/Co3O4 composite electrodes showed higher specific capacitance values and better cycling stability than CuO/Co3O4 composite ones.