A novel process for preparing ZnO nanorods on a Si (I 11) or (10 0) substrate by ion complex transformed PVA-assisted nucleation is presented in this paper. This process involves two steps: highly regular Zn(OH)(2) on a Si substrate were first synthesized via OH groups on the PVA chains complexed with some of zinc ions in a mixed aqueous solution containing Zn(OOCCH3)(2) or ZnCl2 and then the synthesized Zn(OH)(2) decomposed into ZnO nanoseeds at temperature of about 125 degrees C which grew gradually up into ZnO nanorods on the substrate in zinc and oxygen vapors at temperature of 400-600 degrees C. The results of XRD, FE-SEM indicate that the ZnO nanorods are rather evenly distributed on the substrate and possess a single crystal hexagonal wurtzite structure with preferred c-axis orientation. The room temperature PL spectra of the ZnO nanorods exhibit a strong UV emission of about 386 nm and a weak green emission of around 506 nm. The structural and optical characteristics indicate that the ZnO nanorods by this processing are of high crystal quality. (c) 2006 Elsevier B.V. All rights reserved.