A gradual change in morphology of poly(vinylidene fluoride)-camphor sulfonic acid (PVF2-CSA) blend from compact spherulites of PVF2 to open spherulites and finally to giant spherulites with increasing CSA concentration in the blend is observed when viewed in optical microscopy. An X-ray study indicates the presence of two types of lamella, viz., (i) supramolecularly organized lamella of the PVF2-CSA system and (ii) lamella of pure PVF2 crystal in the blends. A differential scanning calorimetry study reveals that the crystallization of the supramolecular organized structure is a slow process Supramolecular organization of PVF2-CSA blends produces giant spherulites at CSA-rich compositions. The giant spherulites contain a fibrillar network structure with the piezoelectric form Of PVF2 and may find application as a sensor material.