A novel heterostructure of PbO2 tipped Co3O4 nanowire arrays (NWs) is fabricated by the combination of hydrothermal synthesis and electrochemical deposition. The hydrothermal process is used to fabricate the Co3O4 nanowire arrays (NWs) on the Ti sheet substrates, and subsequently the PbO2 nanoparticles were preferentially adhered on the sharptip of Co3O4 NWs using an electrochemical deposition method. It is found that the as constructed PbO2/Co3O4 composites exhibit large electroactive areas, low charge transfer resistance, high efficiency regarding the generation of hydroxyl radicals. The photoelectrochemical (PEC) properties of as-constructed PbO2/Co3O4 composites were evaluated by the decolorization of dye (reactive brilliant blue KN-R) in aqueous solution. The PEC measurement indicated that as-constructed PbO2/Co3O4 composites have higher PEC acitivity, better reproducibility and obvious photoelectric synergism, as compared with bare Co3O4 NWs. The promoted PEC ability for the PbO2/Co3O4 composites can be ascribed to the construction of heterointerface between PbO2 and Co3O4. The present work offered attractive perspectives for applications of the PbO2 tipped Co3O4 NWs in the photoanode regarding the treatment of refractory organic pollutant.