Monoclinic　BiVO4　single-crystallites　with　a　polyhedral,　spherical　or　porous　octapod-like　morphology　were　selectively　prepared　using　the　triblock　copolymer　P123　(HO(CH2CH2O)(20)(CH2CH(CH3)O)(70)　(CH2CH2O)(20)H)-assisted　hydrothermal　method　with　bismuth　nitrate　and　ammonium　metavanadate　as　metal　source　and　various　bases　as　pH　adjustor.　The　BiVO4　materials　were　well　characterized　and　their　photocatalytic　activities　were　evaluated　for　the　removal　of　methylene　blue　(MB)　and　phenol　in　the　presence　of　a　small　amount　of　H2O2　under　visible-light　illumination.　It　is　shown　that　the　pH　value　of　the　precursor　solution,　surfactant,　and　hydrothermal　temperature　had　an　important　impact　on　particle　architecture　of　the　BiVO4　product.　The　introduction　of　P123　favored　the　generation　of　BiVO4　with　porous　structures.　The　BiVO4　derived　hydrothermally　with　P123　at　pH　3　or　6　possessed　good　optical　absorption　performance　both　in　UV-　and　visible-light　regions　and　hence　showed　excellent　photocatalytic　activities　for　the　degradation　of　MB　and　phenol.　It　is　concluded　that　the　high　visible-light-driven　catalytic　performance　of　the　porous　octapod-like　BiVO4　single-crystallites　is　associated　with　the　higher　surface　area,　porous　structure,　lower　band　gap　energy,　and　unique　particle　morphology.　Such　porous　BiVO4　materials　are　useful　in　the　solar-light-driven　photocatalytic　treatment　of　organic-containing　wastewater.　(C)　2012　Elsevier　B.V.　All　rights　reserved.