This research investigated the changing morphology of silicon (Si)-supported titanium dioxide (TiO 2 ) thin lms with different heating rates and molecular weights (M W ) of the added polyethylene glycol (PEG). The TiO 2 lms were deposited on a Si wafer (100) by sol-gel spin coating with PEG (M W = 6,000 or 35,000 g·mol −1 ) as pore generating agents. Calcination at 450 C completely decomposed all the organic residues in the TiO 2 sol, and the resultant lms were in the anatase phase. The combustion nature of PEG was found to be the main factor controlling the lm s morphology, where the exothermic heat of PEG combustion tended to be higher with increased heating rates and dependent on the type of PEG (extended and folded chain crystal). At heating rates of 10 C·min −1 or higher, the exothermic heat led to localized grain coalescence in the TiO 2 lms, which decreased the lm porosity. However, this exothermic heat also simultaneously induced pore agglomeration. Hence, the average pore size of PEG-containing lms were larger than in lms without PEG. In contrast, the heating rate did not signicantly affect the morphology lms without PEG.