ZnO has a wide direct band gap of 3.37 eV and a large exciton binding energy of 60 meV at room temperature, which is recognized as one of the promising semiconductors for optoelectronic device applications. However, ZnO generally displays visible defect-related deep-level emission and/or UV near-band-edge emission, which is strongly dependent on the growth method and condition. It has been reported that doping with IIIA elements can improve the optical properties of ZnO. Among them, Ga doping is considered not to induce large lattice distortion of ZnO due to the fact that the bonding lengths of Ga-O and Zn-O are similar and ionic radii of Ga3+ and Zn2+ are also similar. The gallium related compounds such as triethylgallium, gallium nitrate and gallium oxide are used as the Ga doping sources. It has been proved that ZnO film can be grown directly by the thermal oxidation of ZnS substrate. In this research, the Ga doping is adopted in the growth of ZnO film by applying the molten gallium to the surface of ZnS substrate and performing the subsequent thermal oxidation in the air at 650 and 700 °C for 3 and 8 h, respectively. The effects of growth condition on the microstructures and photoluminescence properties of the Ga-doped ZnO film are investigated by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and photoluminescence at room temperature. In addition, the relationship among the oxidation temperature, oxidation time, Ga doping content and photoluminescence properties is discussed. The results show that the Ga-doped ZnO films grown under different growth conditions exhibit various amounts of Ga content and the gallium is present in the ZnO matrix as Ga3+ by partially substituting Zn2+. The Ga doping affects the microstructure and photoluminescence property by changing the defect type and level, stoichiometric ratio, and crystal quality of ZnO film. As the oxidation temperature increases, the amount of Ga doping content increases. In addition, the grain size of the Ga-doped ZnO film increases and becomes uniform, and the ratio of ultraviolet emission intensity to visible emission intensity increases. However, as the oxidation time increases, the amount of Ga doping content decreases, the grain size of the Ga-doped ZnO film becomes non-uniform, and the ratio of ultraviolet emission intensity to visible emission intensity decreases.