In this study, the Cu2Zn1-xCoxSnS4 (CZn1-xCoxTS) films with partial cation substitution of cobalt are synthetized by sol gel spin coating, followed by sulfurization treatment. The incorporation of cobalt cation in the CZTS crystalline lattice as well as the phase transition from kesterite to stannite were confirmed by the X-ray diffraction (XRD) and Raman spectroscopy data. The XRD pattern shows peak-shifting toward higher 2θ by increasing the Co concentration, indicating a decrease in lattice parameters. The red shift of Raman peaks by increasing x from 0 to 0.6, confirms the phase transition. The CZn1-xCoxTS morphology was observed by scanning electron microscopy, showing large grain size as x increases and a good distribution of elements for all films. X-ray photoelectron spectroscopy was employed to study the valence of cations/anions and to probe the chemical bonds. The optical band gap showed a parabolic behavior versus the molar ratio Co/(Co + Zn), this deviation from Vegard’s law being induced by the difference in electronegativity between cobalt and zinc. The pure CZTS has a band gap of 1.47 eV, while for CZn0.6Co0.4TS the gap is 1.17 eV, which indicates that the incorporation of cobalt cation produces a red-shift of the band to band transition energy.