In this research, undoped aluminum sulfide (Al2S3) and with various antimony (Sb) doping concentrations of 2.0, 4.0, 6.0, and 8.0 wt% were synthesized by an electrodeposition method. The α-Al2S3 phase of the hexagonal crystal structure was revealed using x-ray diffraction analysis. The crystallographic parameters of the electrodeposited thin films, for example crystallite size (D), dislocation density (δ), and microstrain (ε) were determined. The transmittance and reflectance spectra were further analyzed for linear, dispersion, optoelectrical, and nonlinear optical properties. The overall optical results were changed with various Sb doping concentrations, owing to the natural formation, and the dependence upon the amount of sulfur or sulfur deficiency in the undoped and Sb-doped Al2S3 thin films. Furthermore, the investigation of major charge carriers in the electrodeposited thin film revealed that the pure Al2S3 exhibited a p-type semiconductor, and the films were altered to be an n-type semiconductor after Sb doping. This demonstration can confirm that this kind of thin film is suitable for promising linear, and nonlinear optoelectronic devices. However, further improvement is required for certain applications in all optical switching or wavelength/photon energy conversions.