Copper tin sulfide/reduced graphene oxide (CTS/RGO) composites are facile synthesized via a simple one-pot hydrothermal route using ethylenediamine tetraacetic acid disodium salt (EDTA-Na2) as a chelating agent. The results of Raman spectra and Fourier transform infrared (FTIR) spectra demonstrate that graphite oxide (GO) sheets are in situ reduced to a certain extent. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations indicate that CTS microspheres, with an average diameter of 450nm around, are anchored on RGO sheets. Electrochemical tests show the CTS/RGO composites exhibit an extraordinary capacity of 1514.6 mAh g−1 with a higher initial coulombic efficiency, excellent cycling stability and better rate capability compared to Cu2SnS3 hollow microspheres (CTS-HMSs) prepared by a similar route in the absence of GO. The enhancement in the electrochemical performance can be attributed to the introduction of RGO sheets that not only accommodate the volume changes and therefore bring the structural integrity of electrode materials, but also provide a highly conductive network for rapid electron transport in electrode during electrochemical reaction.