The Co3O4/AAO composite with novel morphology was successfully prepared by the solution-dipping method and the calcination of cobalt acetate precursor at 400 掳C for 2 h in air. Porous anodic alumina (AAO) thin film was selected as new substrate to support colloidal monolayer template. Scanning electron microscopy (SEM) analysis indicated that the morphology of the as-prepared product could be controlled by changing the concentration of precursor. Catalytic test shows that the obtained Co3O4/AAO composite has a high decolorization ratio in the degradation of methylene blue (MB), which reaches 97.79% in 140 min in the presence of sodium borohydride (NaBH4). Comparative experiments show that this nanomaterial has enhanced catalytic performance.