Cu2ZnSnS4 (CZTS) was obtained from a sol-gel precursor which consists of copper chloride, zinc chloride, tin chloride, and thiourea. CZTS thin films were prepared by spin-coating the sol-gel precursor followed by annealing in a nitrogen atmosphere. The morphology, composition, and structure of the absorber layer were studied by scanning electron microscopy, energy dispersive spectroscopy, x-ray diffraction, and Raman scattering. The optical measurement shows the bandgap of these films is ∼1.51 eV, and the optical absorption coefficient is on the order of 104 cm−1. CZTS solar cells with a structure of low-alkali glass/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Al grid were tentatively fabricated. The best solar cell showed a short-circuit current density of 5.06 mA/cm2, an open-circuit voltage of 358 mV, a fill factor of 34.66%, and an efficiency of 0.63% under AM1.5 (100 mW/cm2) illumination. These results demonstrate the CZTS thin films were successfully deposited by a cheap sol-gel technique.