Phase change materials offer enormous potential for thermal energy storage due to their high latent heat and chemical stability. Researchers have developed numerous innovative strategies to overcome the leakage of organic phase change materials and enhance thermal performance. However, the manufacture of form-stable, free-standing energy storage films based on phase change materials with high latent heat remains difficult. Therefore, the present study focused on the production of free-standing, form-stable energy storage films with high phase change enthalpy and thermally stimulant multiresponsiveness from the simple composite of paraffin with a polytetrafluoroethylene/silica (PTFE/SiO2) aerogel framework, where paraffin was effectively confined in PTFE/SiO2. The resulting paraffin/PTFE/SiO2 films exhibited a large phase change enthalpy (128 J/g) at a paraffin content of 62.8 wt %. The temperature dependent wettability, transmittance, and mechanical properties of this composite film have also been investigated.