We have developed multifunctional nanohybrids of poly(vinylidene fluoride-co-chlorotrifluoroethylene) (CTFE) with a small percentage of surface modified inorganic layered silicate showing dramatic improvement in toughness, radiation resistant and piezoelectric properties vis-à-vis pristine polymer. Massive intercalation (d(001) 1.8 → 3.9 nm) of polymer inside the nanoclay galleries and unique crystallization behavior of the fluoropolymer on the surface of individual silicate layer has been reported. Toughness in the nanohybrid increases more than three orders of magnitude as compared to pure CTFE. High energy radiation (80 MeV Si(+7)) causes chain session, amorphization and creates olefinic bonds in the pure polymer while the nanohybrids are radiation resistant at a similar dose. Nanoclay induces the metastable piezoelectric β-phase in CTFE, suitable for sensor and actuator application. Molecular level changes after irradiation and controlled morphology for smart membrane have been confirmed by using spectroscopy, sol-gel technique, surface morphology studies and in situ residual gas analysis.