Structural　design　and　morphological　control　of　semiconductors　is　considered　to　be　one　of　the　most　effective　ways　to　improve　their　photocatalytic　degradation　properties.　In　the　present　work,　a　hexagonal　WO3　center　dot　0.33H(2)O　hierarchical　microstructure　(HWHMS)　composed　of　nanorods　was　successfully　prepared　by　the　hydrothermal　method.　The　morphology　of　the　HWHMS　was　confirmed　by　field-emission　scanning　electron　microscopy,　and　X-ray　diffraction,　Raman　spectroscopy,　and　thermogravimetric　analysis　demonstrated　that　the　synthesized　product　was　orthorhombic　WO3　center　dot　0.33H(2)O.　Owing　to　the　unique　hierarchical　microstructure,　the　HWHMS　showed　larger　Brunauer-Emmett-Teller　(BET)　surface　and　narrower　bandgap　(1.53　eV)　than　the　isolated　WO3　center　dot　0.33H(2)O　nanorods.　Furthermore,　the　HWHMS　showed　enhanced　photocatalytic　activity　for　degradation　of　methylene　blue　under　visible-light　irradiation　compared　with　the　isolated　nanorods,　which　can　be　ascribed　to　the　narrower　bandgap,　larger　BET　specific　surface　area,　and　orthorhombic　phase　structure　of　the　HWHMS.　This　work　provides　a　potential　protocol　for　construction　of　tungsten　trioxide　counterparts　and　materials　similar　to　tungsten　trioxide　for　application　in　gas　sensors,　photocatalysts,　electrochromic　devices,　field-emission　devices,　and　solar-energy　devices.