In　the　current　work,　a　simple　approach,　directly　mixing　Bi　2O　3　powder　with　TiO　2　sol,　was　developed　to　fabricate　Bi-doped　TiO　2　photocatalyst.　The　obtained　product　was　characterized　by　powder　X-ray　diffraction　(XRD),　transmission　electron　microscopy　(TEM),　Raman　spectra　analysis,　X-ray　photoelectron　spectra　(XPS)　and　UV-vis　diffuse　reflectance　spectroscopy　(DRS).　On　the　basis　of　the　above　characterization　results,　it　was　found　that　the　excess　Bi　2O　3　loading　(>5mol%)　and　sol-gel　processing　route　could　lead　to　the　formation　of　Bi　xTiO　y.　The　XRD　data　pointed　out　that　Bi　xTiO　y　remained　amorphous　up　to　500°C　and　crystallized　into　the　distinctive　phase　Bi　2Ti　4O　11　at　higher　temperature　of　700°C.　It　was　worth　mentioning　that　the　participation　of　the　distinctive　microstructures　made　the　finishing　point　of　the　doped　photocatalyst,　that　is,　strong　spectral　response　in　visible　region　and　marked　activity　during　the　photooxidation　of　gaseous　benzene　under　visible　light　illumination　(λ>450nm).　Furthermore,　the　calcination　temperature　also　had　an　important　effect　on　the　photocatalytic　activity.　The　optimal　dosage　of　10mol%　Bi　in　TiO　2　and　sintering　temperature　of　400°C　achieved　the　best　photocatalytic　activity.　Finally,　the　amorphous　Bi　xTiO　y　microstructures　formed　in　TiO　2　crystal　made　a　significant　contribution　in　providing　large　specific　surface　area　and　more　activated　units　regarding　the　photocatalytic　process.　It　is　hoped　that　our　current　work　will　contribute　to　a　better　understanding　of　the　existence　form　of　bismuth　in　TiO　2　crystal.　More　generally,　it　suggests　the　incorporation　of　bismuth　into　a　simple　oxide　of　wide　band　gap　as　a　strategy　to　design　photocatalysts　with　excellent　properties.　©　2012　Elsevier　B.V.