Highly transparent ZnO semiconductor thin films were deposited onto alkali-free glass substrates by a sol-gel spin coating process. This research investigated the effects of different preheating rates (4 or 10°C/min) on the various surface morphologies, crystallization characteristics, and optical properties of these thin films. The ZnO sol was synthesized by dissolving the zinc acetate dihydrate in isopropanol (IPA), and then adding monoethanolamine (MEA). These as-coated films were preheated at 300°C for 10 min and annealed in an air ambiance at 500°C for 1 h. Experimental results revealed that the as-prepared films had a hexagonal wurtzite structure, and that the heating rates of the preheating process obviously affected the surface morphologies, crystallization qualities, and transparency levels of the thin films. A ZnO thin film preheated at 10°C/min exhibited preferential orientation along the (002) plane, a flat surface, and also achieved a high transmittance value, 92.5%, for light with a wavelength of 550 nm.