Novel　hierarchical　architectures　of　Sb2WO6　are　synthesized　successfully　by　a　simple　hydrothermal　process　without　any　organic　solvent　or　surfactant.　The　physicochemical　properties　of　the　as-prepared　products　are　characterized　in　detail.　Interestingly,　the　morphologies　of　Sb2WO6　could　be　selectively　controlled　by　adjusting　pH　values　of　the　reactive　solutions.　The　tuft-like,　cockscomb-like,　and　flower-like　hierarchical　architectures　are　obtained　at　pH　=　1,　3,　and　5,　respectively.　Based　on　the　time-dependent　experimental　results,　a　possible　growth　mechanism　is　proposed,　which　reasonably　follows　a　synergy　interaction　of　reaction-crystallization　and　dissolution-recrystallization　processes.　The　photocatalytic　activities　of　the　novel　hierarchical　Sb2WO6　are　evaluated　by　the　decomposition　of　azo　compounds　for　the　first　time.　Results　show　that　the　as-prepared　samples　exhibit　the　excellent　photocatalytic　activity　and　universality　for　the　reduction　of　azo　compounds.　The　conversion　of　methyl　orange　reaches　98　%　after　140　min　of　light　irradiation.　HPLC-MS　indicates　that　the　selectivity　of　4-aminobenzene　sulfonic　acid　is　over　99　%.