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A boron nitride nanotube (BNNT), an electrically-insulating counterpart of a carbon nanotube (CNT), is a great nanofiller candidate for ferroelectric polymeric nanocomposites due to BNNT?s exceptional properties in piezoelectricity, thermal stability, mechanical strength, and radiation shielding capability. Fast and high-yield polar crystallization of polyvinylidene fluoride (PVDF) was accomplished by incorporating BNNTs as a nucleating agent. As-fabricated BNNT-PVDF nanocomposites were characterized by Fourier-transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (XRD), and differential scanning calorimetry (DSC) to identify and quantify chain conformations. Besides, piezoelectric constants, d33 of BNNT-PVDF nanocomposites were measured and compared with that of a mechanically drawn beta phase polar PVDF. The polar transformation due to BNNT incorporation has a great advantage over conventional beta or gamma transformation methods that require (1) mechanical drawing often resulting in defects or (2) high-temperature annealing for an extended time. In addition to the fast polar crystallization, BNNTs had a role of reinforcement of the polymer matrix. The improved Young?s modulus and electromechanical coupling coefficient of BNNT-PVDF nanocomposites indicated potential applications in energy harvesting under harsh environments such as large deformation, wide temperature cycles, and high radiation.