The crystal quality is the key to determining the absorption efficiency of the copper-zinc-tin-sulfur-selenium (Cu2ZnSn(S,Se)4, CZTSSe) absorber layer thin film, and spin coating is the first step in the preparation of the CZTSSe absorber layer by solution method, therefore, the choice of the spin coating method is crucial. To explore the effects of different spin coating modes on the quality of CZTSSe absorber layer thin film and the performance of corresponding devices, three groups of copper-zinc-tin-sulfur (Cu2ZnSnS4, CZTS) precursor thin films were prepared by different spin coating modes and the effects of different spin coating modes on the crystal structure, element composition, phase purity and surface morphology of CZTSSe absorber layer thin films were analyzed by X-ray diffractometer (XRD), energy dispersive spectrometer (EDS), Renishaw Raman system (Raman), and field emission scanning electron microscope (FE-SEM), separately. At the same time, the photoelectric characteristics of the CZTSSe thin film solar cell were characterized by current density-voltage (J-V) characteristic and external quantum efficiency (EQE) tests. The results show that the spin coating mode with 7 cycles and 2 times spin coatings before each baking in the first cycle result in uniform CZTS precursor thin films without cracks, higher crystallinity of CZTSSe absorber layer thin films, flatter, and denser film surface, and more uniform grain size. As a result, the CZTSSe thin film solar cell with a photoelectric conversion efficiency of 9.63% is realized. Through the statistical analysis of the performance parameters of devices based on different spin coating modes, it concludes that the new spin coating modes can improve the repeatability of CZTSSe thin film solar cells and pave the way for possible large-scale commercial applications in the future.