Multilayer ZnO films fabricated by the combination of sol-gel and aqueous solution deposition routes exhibit many flowerlike clusters with the diameter of 2-4 mu m on their top layer. Each flowerlike cluster is an assembly of nanoparticles 20-30 nm in diameter. The investigation of electrochemical properties, phase, and composition of the ZnO film before and after cyclic voltammetric measurement revealed that the reaction mechanism of lithium with ZnO in our growth method differs from those from the literature. The proposed reversible electrochemical reactions would potentially cause the improvement of capacity retention and the enhancement of cycling performance, which might break the reported negative conclusions such as poor cycling on lithium storage in ZnO. (C) 2009 The Electrochemical Society. [DOI: 10.1149/1.3089368] All rights reserved.