ZnO nanorod arrays were synthesized on glass substrates coated by a ZnO seeding layer via a hydrothermal technique by adding polyethyleneimine (PEI) to the growth solution. The XRD and SEM results show that the ZnO nanorods have the single crystal wurtzite structure with the (0 0 2) direction normal to the substrates. In 50 ml growth solution of 0.05 M zinc salts, the average diameter of the nanorods was reduced drastically from 300 nm to 40 nm with the PEI amount increasing from 0 ml to 6 ml. The diameter distribution and the polycrystalline layer at the bottom of the nanorods were improved. Longer nanorods were obtained by prolonging the growth time. Based on the results, possible mechanisms that PEI adsorbs on the non-polar facets of ZnO nanorods and its coordination to zinc ions were proposed to elucidate the effect of PEI on reducing the diameters and improving the morphologies of nanorods. (C) 2007 Elsevier Ltd. All rights reserved.