This research focus on the effect of polyethylene glycol (PEG) on TiO2 thin film. Sol-gel method is the best method which tends to be used due to its simplicity, good chemical homogeinity and high purity of the product. Titanium (IV) isopropoxide, isopropanol and acetic acid are the three different chemical which being used to make sol solution. The samples was then will annealed at three different temperature which are 400 °C, 500 °C and 600 °C to observed the phase composition of TiO2 added PEG thin film and pure TiO2 by using X-ray diffraction (XRD) analysis and the structural surface by using scanning electron microscope (SEM) analysis. The XRD analysis show the anatase phase present for the sample of pure TiO2 thin film and rutile phase present for the sample of TiO2 added PEG thin film. The micrograph of SEM show that with the addition of PEG at high temperature will give the analysis of flaky large cracked which is not separated to each other on the surface coating. Meanwhile, pure TiO2 give the result of irregular shape structure of the film.