Cu₂ZnSn(S, Se)₄(CZTSSe) thin films were deposited on flexible substrates by three evaporation processes at high temperature. The chemical compositions, microstructures and crystal phases of the CZTSSe thin films were respectively characterized by inductively coupled plasma optical emission spectrometer (ICP-OES), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman scattering spectrum. The results show that the single-step evaporation method at high temperature yields CZTSSe thin films with nearly pure phase and high Sn-related phases. The elemental ratios of Cu/(Zn+Sn)=1.00 and Zn/Sn=1.03 are close to the characteristics of stoichiometric CZTSSe. There is the smooth and uniform crystalline at the surface and large grain size at the cross section for the films, and no other phases exist in the film by XRD and Raman shift measurement. The films are no more with the Sn-related phase deficiency.