Structure-properties relationships in poly(vinylidene fluoride-co-hexafluoropropylene), PVDF-HFP, clay nanocomposites are reported for the first time. Addition of organically modified clays to PVDF-HFP promotes an α to β transformation of the polymer crystals. The degree of transformation depends on the nature of the clay surface modifier and scales with the strength of the interactions between the clay and the polymer. The nanocomposites exhibit significant increases in elongation to failure compared to the neat copolymer. In addition, their dielectric permittivity is higher over a wide temperature range. Their mechanical and dielectric properties scale similar to the amount of the β phase present in the nanocomposites.