Gallium phosphide nanowires were successfully synthesized by the catalytic chemical vapor deposition (CVD) method using MgO powder-impregnated nickel oxide as catalyst and gallium phosphide and gallium powders as GaP source. The synthesis of GaP nanowires were carried out at 900°C for 30min under argon ambient and directly vaporized Ga and GaP powder. The diameter of GaP nanowires is about 25~70nm and the length is up to several tens of micrometers. The GaP NWs was core-shell structure, which consists of the GaP core and the Ga oxide outer layers. The GaP nanowires have a single-crystalline zinc blend structured crystals with the  growth direction. Nanowires larger than around 50nm in diameter exhibited twinning faults, which appears in the TEM images as discrete dark lines and alternating wire contrast. We demonstrate that MgO powder-impregnated nickel oxide catalyst exhibited a large catalytic effect on the growth of high-purity and -quantity gallium phosphide(GaP).