Melon-seed-shaped LiFePO4 hollow micro- and sub-micrometer plates have been synthesized via a polyol-assisted hydrothermal method. The as-prepared LiFePO4 hollow materials were new with regard to their single-crystalline shells with large ac surfaces. Based on the detailed analysis of time-dependent studies, a possible growth mechanism was proposed involving nucleation, anisotropic growth, selective etching, and reversed recrystallization. The effects of polyol concentration, reaction temperature, and feeding sequence of precursors on the growth of LiFePO4 materials were investigated. The electrochemical properties of as-prepared LiFePO4 hollow materials were examined as cathode materials.