Polytetrafluoroethylene (PTFE) is a polymer that displays exceptional properties. This synthetic fluoropolymer is also known to crystallize very fast upon cooling. The present work highlights for the first time the influence of nanosilica clusters on PTFE crystallization at fast cooling rates (up to 5000 K·s−1). The silica was synthesized from aqueous silicate solution and the surface modification was performed using TriEthoxyFluoroSilane (TEFS). In order to understand the crystallization behavior of PTFE/silica nanocomposite at a fast cooling rate, the measurements were carried out by Fast Scanning Calorimetry (FSC). The data were consequently combined with the measurements performed by conventional Differential Scanning Calorimetry (DSC). Interestingly, the results displayed variation of the crystallization behavior for the nanocomposite at fast cooling rates compared to slow cooling rates. The differences in crystal morphologies were then observed by Scanning Electron Microscopy (SEM) after slow and fast cooling rates. Finally, the effective activation energies (Eα) obtained from the crystallization under various cooling rates were combined in order to obtain one set of Hoffman-Lauritzen parameters. This procedure allowed us to show that the crystallization of PTFE in the presence of silica is promoted or hampered according to the cooling rates employed.