ZnS films have been deposited on glass substrates by chemical bath deposition (CBD). The optical and structural properties were analyzed by UV-VIS spectrophotometer and X-ray diffraction (XRD). The results showed that the prepared thin films from the solution using N2H4 as second complexing agent were thicker than those from the solution without adding N2H4 in; this is due to using second complexing agent of N2H4, the deposition mechanisms change which is conductive to heterogeneous deposition. When using N2H4 as second complexing agent, the crystallinity of ZnS thin films improved with a significant peak at 2θ=28.96°which can be assigned to the (111) reflection of the sphalerite structure. The transmittances of the prepared films from the solution adding N2H4 in as second complexing agent were over 85%, compared to those from the solution without N2H4 (over 95%). The band gaps of the ZnS films from the solution using N2H4 as second complexing agent were larger (about 4.0eV) than that from those from the solution without N2H4 (about 3.98eV), which indicated that the prepared ZnS films from the solution adding N2H4 in as second complexing agent were better used as buffer layer of solar cells with adequate optical properties. In short, using N2H4 as second complexing agent, can greatly improve the optical and structural properties of the ZnS thin films.