The　three-dimensionally　ordered　macroporous　(3DOM)　BiVO4　and　its　supported　iron　oxide　(xFe(2)O(3)/3DOM　BiVO4,　x=0.18,　0.97,　and　3.40　wt%)　photocatalysts　were　prepared　using　the　ascorbic　acid-assisted　polymethyl　methacrylate-templating　and　incipient　wetness　impregnation　methods,　respectively.　Physicochemical　properties　of　the　materials　were　characterized　by　means　of　numerous　analytical　techniques,　and　their　photocatalytic　activities　were　evaluated　for　the　degradation　of　4-nitrophenol　under　visible　light　illumination.　It　is　found　that　the　BiVO4　possessed　a　high-quality　3DOM　architecture　with　a　monoclinic　crystal　phase,　and　the　Fe2O3　was　highly　dispersed　on　the　surface　of　3DOM　BiVO4.　The　xFe(2)O(3)/3DOM　BiVO4　samples　much　outperformed　the　3DOM　BiVO4　sample,　and　0.97Fe(2)O(3)/3DOM　BiVO4　showed　the　best　photocatalytic　performance　(98%　4-nitrophenol　was　degraded　in　the　presence　of　0.6　mL　H2O2　within　30　min　of　visible　light　illumination)　and　excellent　photocatalytic　stability.　The　introduction　of　H2O2　to　the　reaction　system　could　promote　the　photodegradation　of　4-nitrophenol　by　providing　the　active　(OH)-O-center　dot　species　generated　via　the　reaction　of　photoinduced　electrons　and　H2O2.　The　pseudo-first-order　reaction　rate　constants　(0.0876-0.1295　min(-1))　obtained　over　xFe(2)O(3)/3DOM　BiVO4　were　much　higher　than　those　(0.0033-0.0395　min(-1))　obtained　over　3DOM　or　Bulk　BiVO4　and　Fe2O3/Bulk　BiVO4,　with　the　0.97Fe(2)O(3)/3DOM　BiVO4　sample　exhibiting　the　highest　rate　constant.　The　enhanced　photocatalytic　performance　of　0.97Fe(2)O(3)/3DOM　BiVO4　was　associated　with　its　unique　porous　architecture,　high　surface　area,　Fe2O3　-　BiVO4　heterojunction,　good　light-harvesting　ability,　high　adsorbed　oxygen　species　concentration,　and　excellent　separation　efficiency　of　photogenerated　electrons　and　holes　as　well　as　the　photo-Fenton　degradation　process.　(C)　2016　Elsevier　B.V.　All　rights　reserved.