Randomly oriented poly(vinylidene fluoride) (PVDF) nanofibre webs prepared by a needleless electrospinning technique were used as an active layer for making mechanical-to-electrical energy harvest devices. With increasing the applied voltage in the electrospinning process, a higher beta crystal phase was formed in the resulting PVDF nanofibres, leading to enhanced mechanical-to-electrical energy conversion of the devices. The power generated by the nanofibre devices was able to drive a miniature Peltier cooler, which may be useful for the development of mechanically driven cooling textile. In addition, the needleless electrospinning also showed great potential in the production of nanofibres on a large scale.