Silicon nanowires are important semiconductor with core/shell structure. In this work, the piezoelectric material alpha-quartz was grown in the interface of silicon nanowires by thermal treatment at 600 °C for 0.5 h. These nanowires were employed as starting materials to fabricate piezoelectric nanogenerators, which could convert kinetic energy into electrical one, exhibiting an output voltage of 36.5 V and a response current of 1.4 μA under a free-falling object of 300 g at a height of 30 cm.