Novel chrysanthemum-like hierarchical microstructures of orthorhombic InVO4 were synthesized via a hydrothermal route without assistance of any template or organic additive. The chrysanthemum-like InVO4 microstructures are built up of numerous nanobelts radially aligned around the spherical surface. Based on the structural feature of orthorhombic InVO4 and the key role of the pH value, a probable mechanism of the etching-splitting growth process induced by H+ ions was proposed to explain the formation of InVO4 microstructures. Furthermore, the chrysanthemum-like InVO4 sample shows a high discharge capacity of 608.6 mAh g(-1) and acceptable capacity retention when used as an electrode material in lithium ion batteries. The pure orthorhombic phase and unique porous morphology play basic roles in the structural requirement to serve as transport paths for lithium ion. (C) 2010 Elsevier Ltd. All rights reserved.