To prepare coatings with enhanced self-cleaning properties, organic− inorganic hybrid materials were constructed that are composed of a polymer (poly(vinylidene fluoride)) with embedded particles (TiO 2 ) coated with a perfluorinated (C−H bond free) phthalocyanine photosensitizer and also containing the volatile salt ammonium hydrogen carbonate. Coatings prepared from this material were thermolyzed at 80 °C to volatilize the salt. The resulting coatings exhibit enhanced hydrophobicity as demonstrated by contact angles exceeding 150°, a property imparted by the surface roughness generated by gases and vapors released upon the thermal decomposition of the volatile salt. The surface roughening does not hinder the photogeneration of singlet oxygen, as evidenced by the photocatalyzed decomposition of a model dye, methyl orange, present in solutions placed in contact with the coatings. These new materials, which exhibit self-cleaning properties, could thus be useful for repelling pollutants through enhanced hydrophobicity and the lasting, catalytic degradation of contaminants by reactive oxygen species produced from light and air.