We report a novel {001}TiO2/Ti photoelectrode by directly constructing "mirror-like" TiO2 microspheres on a Ti foil substrate (M-{001}TiO2/Ti). It presents highly enhanced PEC oxidation capability of DMP wastewater, which is mainly attributed to the significant synergetic effects of high exposure of {001} facets and equivalent {001}/{101} facet junctions.