The main idea of this study is to figure out the CZTSe thin-film quality by using the hybrid inks of CTSe and ZnSe under the influence of the selenization time. In this study, we provide a sample with low-cost and non-toxic method to get a uniform and good crystallinity thin film. The Cu2ZnSnSe4 (CZTSe) compound layers were grown by using the two-step technique. Firstly, we use the non-vacuum process and solvothermal refluxing method with polyetheramine (D400) as the solvent to prepare the Cu2SnSe3 (CTSe) and ZnSe inks, and then we mixed CTSe with ZnSe inks to turn into the CZTSe hybrid inks. Secondly, the sample was selenized in a two-temperature zone closed quartz reactor with a saturated selenium atmosphere, and then a flowing Nitrogen gas is maintained to deliver a constant supply of Se vapor during the process. After the two-step technique, the morphology, structure and optical properties of CZTSe thin films was obtained by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), Ultraviolet–visible spectroscopy (UV-vis) and Raman scattering spectrum, respectively.