Bismuth　(Bi)-doped　silica-based　glasses　and　fibers　are　attractive　materials　for　the　new　optical　amplifiers　and　tunable　lasers.　In　this　paper,　Bi/Al　co-doped　silica　glass　with　a　relatively　high　Bi　concentration　(0.552　wt.%)　were　prepared　by　using　the　optimized　sol-gel　method.　Hydrofluoric　acid　(HF)　was　used　as　a　catalyst　in　the　reaction,　which　reduced　the　hydroxyl　to　lower　than　5ppm　in　the　final　glass.　After　the　process　of　drying　and　sintering,　the　gel　was　turned　into　the　transparent　glass　at　low　temperature　(~1300　°C).　The　optical　properties　of　Bi/Al　co-doped　silica　glass　were　also　investigated.　Excited　by　a　980　nm　laser　diode　(),　broadband　fluorescence　centered　at　1114　nm　was　obtained,　which　was　ascribed　to　the　Bi-Al　active　center　(BAC-Al).　The　emission　cross-section　(σem)　was　calculated　to　be　7.4　×　10−21　cm2　for　BAC-Al.　In　addition,　ultra-broadband　emission　ranging　from　850　nm　to　1700　nm　was　also　obtained　excited　by　the　808　nm　LD,　which　might　be　ascribed　to　BAC-P　overlapped　by　other　BACs.　After　the　gaussian　separation　of　fluorescence　peak,　the　emission　cross-section　for　BAC-P　was　13.4×　10−21　cm2.　Our　results　confirmed　the　potentialities　of　the　optimized　sol-gel　method　in　Bi-doped　glass　fabrication.　The　Bi/Al　co-doped　silica　glass　prepared　in　this　work　were　promising　to　develop　Bi-doped　fibers　and　relative　devices.　©　2023　SPIE.