The photochemical conversion of the zinc oximato complex of di‐aqua‐bis[2‐(methoxyimino)propanoato]zinc 1 into zinc oxide thin films is introduced as an alternative route compared with the traditional thermal process. Irradiation of 1 by UV light produces smoother films with random orientation of crystalline grains, compared with the thermal route, which results in films with a high degree of (002) orientation (texture) toward the substrate. By addition of Ga(NO3)3, gallium‐doped zinc oxide (GZO) thin films can be obtained after further sintering, e.g., in air. The GZO films exhibit a low surface roughness and a high optical transparency. Electrical resistivities as low as 7.4 × 10−2Ω·cm were observed, making it a candidate for application in the field of transparent conduction oxides.