A novel ZnO nanorod array (NR)/CuAlO(2) nanofiber (NF) heterojunction nanostructure was grown on a substrate of Ni plates using sol-gel synthesis for the NFs and hydrothermal reaction for the NRs. Compared with a traditional ZnO/CuAlO(2) laminar film nanostructure, the photocurrent of this fibrous network heterojunction is significantly increased. A significant blue-shift of the absorption edge and a favorable forward current to reverse current ratio at applied voltages of -2 to +2 V were observed in this heterojunction with the increase of Zn(2+) ion concentration in the hydrothermal reaction. Furthermore, the photoelectrochemical properties were investigated and the highest photocurrent of 3.1 mA cm(-2) was obtained under AM 1.5 illumination with 100 mW cm(-2) light intensity at 0.71 V (versus Ag/AgCl). This novel 3D fibrous network nanostructure plays an important role in the optoelectronic field and can be extended to other binary or ternary oxide compositions for various applications.