Morphological　synthesis　of　V2O5/TiO2　nanocomposites　with　unique　core-shell　spherical　nanostructures　and　solid　sphere　nanostructures　were　achieved　by　solvothermal　method　and　hydrothermal　method,　respectively.　Owing　to　their　intrinsic　semiconductive　properties　and　different　nanostructures,　both　of　these　two　nanocomposites　were　employed　as　solar　energy　transducers　to　photo-oxidation　of　arsenic　(III)　in　aqueous　solution,　with　the　purpose　to　better　understanding　the　morphological　effect　in　photocatalysis.　It　clearly　demonstrated　that　V2O5/TiO2　with　core-shell　spheres　morphology　exhibited　an　excellent　photocatalytic　activity　in　the　oxidation　of　arsenite　(about　92%),　remarkably　superior　to　the　one　with　solid　sphere　nanostructure,　because　of　its　larger　specific　surface　area,　enhanced　visible　harvest　ability　and　improved　charge　separation　efficiency.　Furthermore,　we　discovered　that　superoxide　radicals　and　photo-generated　holes　are　the　active　species　responsible　for　the　oxidation　of　As(III)　in　the　V2O5/TiO2　photocatalytic　system.　©　2015　Elsevier　B.V.