For the first time, a nanocomposite of poly(vinylidene fluoride)/cellulose nanocrystal (PVDF/CNC) is developed as a piezoelectric energy harvester. This is implemented through electrospinning of PVDF solutions containing different levels of CNC loading, i.e., 0, 1, 3 and 5 % with respect to PVDF weight. Analytical techniques including DSC, FTIR and WAXD are conducted to monitor the polymorphism evolution within electrospun nanocomposites as the CNC content is varied. The results imply that CNCs at the optimum concentration (3 and 5 %) can effectively nucleate beta crystalline phases. The nucleation of alpha crystalline phases is also prevented when CNCs are present within the structure of PVDF electrospun fibers. These changes in polymorphism give PVDF/CNC nanocomposites enhanced piezoelectric characteristics compared to pure PVDF nanofibers. We have demonstrated that the developed nanocomposites can charge a 33-mu F capacitor over 6 V and light up a commercial LED for more than 30 s. It is envisaged that the PVDF/CNC nanocomposites provide the opportunity for the development of efficient electrical generators as self-powering devices to charge portable electronics.