Monoclinic　BiVO4　single-crystallites　with　polyhedral,　rod-like,　tubular,　leaf-like,　and　spherical　morphologies　have　been　fabricated　using　the　triblock　copolymer　P123-assisted　hydrothermal　strategy　with　bismuth　nitrate　and　ammonium　metavanadate　as　metal　source　and　various　bases　as　pH　adjustor.　The　physicochemical　properties　of　the　materials　were　characterized　by　means　of　the　XRD,　TGA/DSC,　Raman,　HRSEM,　HRTEM/SAED,　XPS,　and　UV-vis　techniques.　The　photocatalytic　activities　of　the　as-fabricated　BiVO4　samples　were　measured　for　the　photodegradation　of　methylene　blue　(MB)　under　visible-light　irradiation.　It　is　shown　that　factors,　such　as　the　pH　value　of　precursor　solution,　the　introduction　of　surfactant,　the　nature　of　alkaline　source,　and　the　hydrothermal　temperature,　have　a　crucial　influence　on　the　particle　architecture　of　the　BiVO4　product.　Among　the　as-fabricated　BiVO4　samples,　the　ones　derived　hydrothermally　with　P123　at　pH　=　6　or　10　possessed　excellent　optical　absorption　performance　both　in　UV-　and　visible-light　regions　and　hence　showed　outstanding　photocatalytic　activities　for　the　addressed　reaction.　The　unusually　high　visible-light-driven　catalytic　performance　of　monoclinically　crystallized　rod-like　and　tubular　BiVO4　single-crystallites　is　associated　with　the　higher　surface　areas　and　concentrations　of　surface　oxygen　defects,　and　unique　particle　morphologies.　The　possible　formation　mechanisms　of　such　multiple　morphological　BiVO4　materials　have　also　been　discussed.　(C)　2010　Elsevier　B.V.　All　rights　reserved.