Perfluoro-1,3-propanedisulfonic acid (PFPS)/Nafion/silica hybrid particles were prepared by the sol-gel reactions of PFPS with tetraethoxysilane and silica nanoparticles in the presence of Nafion under alkaline conditions. These obtained composites exhibited a good dispersibility and stability in not only water but also traditional organic media such as methanol, ethanol, 1,2-dichloroethane, tetrahydrofuran, and dimethyl sulfoxide. Dynamic light scattering measurements and field-emission scanning electron microscopy show that these hybrid particles are nanometer size-controlled fine particles before and even after calcination at 800 degrees C. Nafion/silica hybrid nanoparticles were also prepared in the absence of PFPS under similar conditions. The weight of original Nafion markedly dropped around 350 degrees C and decomposed gradually, reaching 0% around 450 degrees C, and Nafion in the Nafion/silica nanocomposites exhibited a similar weight loss behavior to that of the original one. However, Nafion/PFPS/silica hybrid nanoparticles were found to exhibit no weight loss corresponding to the contents of Nafion and PFPS in the silica gel matrices even after calcination at 800 degrees C. It was demonstrated that the pH value (3.77 at 25 degrees C) of Nafion/PFPS/silica hybrid nanoparticles after calcination is smaller than that (5.66 at 25 degrees C) before calcination, and this hybrid nanoparticles exhibited a higher proton conductivity (5.8 x 10-3 S/cm at 85 degrees C) than that (4.1 x 10-3 S/cm at 85 degrees C) before calcination. In addition, Nafion/PFPS/silica hybrid nanoparticles after calcination at 800 degrees C were applied to the Friedel-Crafts acylation of thiophene with acetic anhydride to give the expected 2-acetylthiophene, of whose yield was similar to that before calcination under similar conditions. These findings suggest that Nafion in PFPS/silica hybrid nanoparticle cores should exhibit a nonflammable characteristic even after calcination at 800 degrees C to act as an effective acid catalyst. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1869-1877