Facile methods for adjusting crystallinity of poly(vinylidene fluoride) (PVDF) composites filled with nanofillers are disussed in this presentation. The BaTiO3 HNSs of 20 nm in diameter were readily synthesized using SiO2 nanospheres as soft templates, and provided larger surface interaction areas to enhance the β-phase contents. Surface modifiers having different functionalities, such as APTMS, APTES, and TMS, have caused the enhanced molecular interactions. NH2-treated GNDs were readily synthesized by excessive chemical oxidation of CNFs, and the NH2-treated GND/RGO dual cofillers provided the effective dipole polarizations and the nucleation of β-phase crystals of the PVDF.