A simple low-temperature solution-based self-construction approach has been demonstrated for fabricating the highly uniform assembly of ZnO nanocones with much higher aspect ratio, in which a highly non-equilibrium chemical environment favors for the large-scale generation of the complex architectures mimicking the sisal-like structures. The formation mechanism has been studied at molecular level. The optical and photocatalytic properties of the as-synthesized product have been correlated with their chemical composition, morphology and structural features. These sisal-like ZnO nanocone assemblies have shown a strong UV emission with a broad blue emission band and a high photocatalytic activity in decomposition of polyaromatics, suggesting their potentials in light and field emission and environmental applications. (c) 2006 Elsevier B.V. All rights reserved.