In this paper, the Cu2SnS3 hollow microspheres (CTS-HMSs) have been successfully synthesized via a hydrothermal route, in which ethylenediaminetetraacetic acid disodium salt (EDTA-Na-2) is introduced as both a chelating agent and a template. X-ray diffraction (XRD) results indicate that EDTA-Na-2 plays crucial roles in determining the phase of Cu2SnS3 products, and the morphological characterizations show that the shell thickness of hollow microspheres is about 0.2 mu m and the outer diameter is in the range of 1.0-12 mu m. In particular, charge-discharge performance and cycle performance for the novel CTS-HMS materials in lithium-ion batteries are preliminarily investigated, and the unique electrode material exhibits a high initial lithium ion storage capacity of 1316 mA h g(-1), suggesting a promising electrode material for lithium ion batteries. (C) 2014 Elsevier B.V. All rights reserved.