In this letter, tungsten oxide(WO3)/TiO2 core-shell nanowires were prepared by depositing a layer of TiO2 nanoparticles on the surface of WO3 nanowires via a pulse laser deposition method. These TiO2 nanoparticles are qusi-aligned wire-like structure on the surface of WO3 nanowires. The number of laser pulses during the deposition adjusts the TiO2 thickness. When used as photocatalyst, these core-shell nanowires have photocatalytic activity in the degradation of rhodamine B (RhB). The photo-induced electron-hole separation effect between WO3 and TiO2 contributes to the improvement of the photocatalystic activity. This makes these nanowire arrays having good potential in wastewater treatment.