Quaternary stannite semiconductor Cu2FeSnS4 (CFTS), which is an ideal material for solar photovoltaic cells, has attracted widespread attention. CFTS crystals have been successfully synthesized by the co-electrochemical deposition method. The structure, morphology, and composition of as-synthesized samples were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), respectively. From the results, it was found that the properties of the sample can be improved by tuning the Cu2+ concentration in the electrolyte, and the best sample was obtained with the Cu2+ concentration of 0.01 M. For the best sample, the CFTS thin films have single phase and good crystallinity with even particle size. By the addition of ascorbic acid, an effective way has been found to enhance the Fe content in the sample, and the reason for the Fe-poor phenomenon has also been explored.