In recent years, the controlled synthesis of inorganic micro- and nanostructures with hollow interiors has attracted considerable attention because of their widespread potential applications. A feasible method for synthesizing Li3VO4 by a template-free, solution synthesis of single-crystalline microboxes with well-defined non-spherical morphologies has been reported. This study provides the useful information to produce other hollow structure materials to the broad audience of readers. The formation of hollow structure and the influence of raw materials have been presented. The thus-synthesized Li3VO4 exhibited significantly improved conductivity, rate capability, and cycling life compared to commercial graphite, synthesized Li4Ti5O12, and previously reported Li3VO4.