Self-assembled nanoporous tungsten oxide (WO3) with preferential orientation (002) planes was successfully synthesized on the tungsten sheet by anodization in a 0.2 wt % NaF and 0.3% (V/V) HF mixture solution in a 1:1 ratio. The pores, of a highly ordered self-assembled structure, had an average size of approximately 70 nm. X-ray diffraction identified a monoclinic WO3 structure and fine preferential orientation of (002) planes. A maximum photoconversion efficiency of 17.2% was obtained for the self-assembled nanoporous WO3 under high-pressure mercury lamp illumination. The photocatalytic (PC) degradation of pentachlorophenol (PCP) in aqueous solution using the self-assembled nanoporous WO3 photocatalyst, performed under both high-pressure mercury lamp and Xe lamp illumination, showed more excellent PC capability than WO3 film and TiO2 nanotube arrays.