The crystalline structure and molecular mobility of poly(vinylidene fluoride) (PVDF) blended with poly(methyl methacrylate) (PMMA) have been investigated using solid-state 19 F magic angle spinning (MAS) NMR spectroscopy. The origin of the characteristic crystalline peaks observed for three typical polymorphs of PVDF (a-, b-and c-forms) are explained based on the density functional theory (DFT) calculations of a model compound. Variations in the crystalline conformation of PVDF chains in the blends, the degree of crystallinity and the molecular mobility in the amorphous phase are quantitatively analyzed using the NMR spectral shapes and the 19 F spin-lattice relaxation time in the rotating frame (T 1q

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