Well-aligned ZnO nanowires (NWs) were successfully synthesized on Si(100) by the process of carbothermal reduction and vapor–liquid–solid method. Scanning electron microscopy and transmission electron microscopy results confirmed that ZnO NWs were single crystalline wurtzite structures and grew along the  direction. The influences of substrate temperature and total pressure on the growth were discussed. The well-aligned ZnO NWs show good field emission properties, and the emitter constructed of pencil-like ZnO NWs exhibited a low turn-on field (3.82 V μm−1) and a high field enhancement factor (β = 2303). Finally, we demonstrated that the as-prepared ZnO NWs with small diameter on the substrate have good photocatalytic activity toward degradation of methylene blue. Using ZnO NWs with Au nanoparticles (NPs) would decrease the recombination rate of hole–electron pairs due to the great shift of the Fermi level to the conduction band. Hence, adding Au NPs was a promising method to enhance the photocatalytic performance of ZnO NWs. It is significant that photocatalyst fabricated by ZnO NWs can apply to the degradation of organic pollution, and solve the environmental issues.