Bismuth sulfide (Bi2S3) is an important semiconductor material, which has wide applications in thermoelectricity, electronics, photoelectricity and infrared spectroscopy. Bi2S3 thin films have been deposited on ITO substrates through a cathodic electrodeposition approach at room temperature. The as-deposited thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence spectrum (PL). The effects of solution pH values on the structures and optical properties of the thin films were particularly investigated. Results show that uniform Bi2S3 thin films with oriented growth along (240) direction can be obtained at the solution pH value range from 4.5 to 6.5. The as-prepared thin films exhibit stable blue-green photoluminescence properties under the ultraviolet light excitation at room temperature. With the increase of the solution pH values, the crystallization of the Bi2S3 thin films improves while the grain size of the obtained thin films decreases and the light emission intensity of the thin films decreases.