Poly(vinylidene fluoride) (PVDF) and cellulose nanocrystals (CNCs) fibrous composites were prepared by electrospinning. Compared with neat PVDF fibers, PVDF/CNCs composites contain higher content of beta phase with help of rod-liked CNCs. The highest content of beta phase among these fibrous membranes is as high as 89.96%. Furthermore, the piezo-voltage generated by the power generator which is made of PVDF/CNCs fibrous composite indicates that addition of CNCs to PVDF fiber matrix contributes to improving piezoelectric performance of PVDF fiber.