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Polyvinyl alcohol (PVA) blending with the phase change material (PCM) to prepare thermal energy storage film has the disadvantage of leakage. The waste fly ash (FA) can be used as the substrate of PCM to prevent leakage and give the FA high value. In this study, the rude fly ash (RFA) with the modification of rinsing and HCl treatment impregnates the stearic acid (SA) directly to prepare rFAS and HFAS, respectively. The PVA/FAS thermal energy storage films are prepared by solution casting. The surface properties and the absorption capacity analysis of the FA indicated that the modification can increase the surface areas and average pore volume and the HFAS have the best adsorption capacity. The results of scanning electron microscopy (SEM) and fourier transform infrared spectroscopy (FTIR) show that the SA successfully adsorbed on the FA. The PVA/FAS thermal energy storage films with the 15% HFAS content have the best tensile strength (9.87 MPa), thermal conductivity (0.611 W*[m.sup.-1]*[K.sup.-1]), and thermal energy storage property (59.04 J*[g.sup.-1] after 1 cycle time) because of the best compatibility between HFAS and PVA. After 500 cycle times, the latent heat of the PVA/HFAS decreased only 4.62% and the PVA/RFAS and PVA/RFAS decreased by 8.32%, and 10.87%, respectively. KEYWORDS phase change materials, polyvinyl alcohol, thermal energy storage films, waste fly ash, 1 | INTRODUCTION Polyvinyl alcohol (PVA) has advantages such as nontoxic, biodegradable, water-soluble, and good film forming properties, which is widely used in the field of food packaging films. [1-3] [...]