A novel structure of hexagonal CuSbS₂ nanobricks were successfully synthesized on the TiO₂ nanorod arrays via a solvothermal method by using polyethylene glycol (PEG) as the morphology-directing agent. The photoelectrochemical properties of TiO₂/CuSbS₂ films were also characterized and discussed. The results revealed that the PEG could be absorbed on the surface of CuSbS₂ nuclei selectively and confine their growth in certain direction. The hexagonal CuSbS₂ nanobricks with the side length of 70 nm and thickness of 30 nm were synthesized from a precursor solution containing Cu⁺, Sb³⁺, S²⁻ and PEG with an optimal Cu:Sb:S:PEG volume ratio of 2:2:4:1. The CuSbS₂ films on the TiO₂ nanorod arrays improved the optical absorption and energy conversion efficiency of the bare TiO₂ nanorods significantly. The enhanced photoelectrochemical performance of TiO₂/CuSbS₂ photoelectrodes was attributed to the enlargement of photoresponse range, increasement of the charge carrier density and the fast separation of photogenerated electron-hole pairs. The results of present work demonstrate further insight for improving the efficiency of semiconductors by using a suitable electron transfer channels, which may be promising for rational construction of solar conversion and storage devices.