We report for the first time a template-free approach for the fabrication of beta-form crystalline poly (vinylidene fluoride) (PVDF) nanowire arrays with hollow structures. The controllable growth of PVDF nanowires was achieved through the high-pressure crystallization of well-dispersed fullerene C60/PVDF nanocomposites, which was prepared by an easy physical and mechanical process. The size and morphology of PVDF nanowires were sensitive to the crystallization conditions, and large scale vertically-aligned piezoelectric nanowire arrays were finally formed by regulating the applied temperature and pressure. This was attributed to a C60-induced self-assembly of the polymer, driven by physical interactions at high pressure. With its unique structures, the as-fabricated PVDF nanowire array may diversify niche applications in harvesting energy for self-powered wireless nanodevices and nanosystems. (C) 2013 Elsevier Ltd. All rights reserved.