A　new　barium　aluminoborate,　Ba6Al4B14O33,　has　been　synthesized　by　the　high-temperature　solution　reaction　at　700　degrees　C.　The　single-crystal　XRD　analysis　showed　that　it　crystallizes　in　a　new　structure　type　with　space　group　PI,　a=7.0070(14)　A,　b=13.880(3)　A,　c　=14.702(3)　A,　alpha=86.48(3)degrees,　beta=88.99(3)degrees,　gamma=83.46(3)degrees,　V=1417.8(5)　A(3),　and　Z=2.　The　fundamental　building　blocks　in　this　structure　are　AlO4　tetrahedra,　BO3　triangles,　[Al4O14](16-)　groups　composed　of　two　AlO4　tetrahedra　and　two　AlO5　trigonal　bipyramids,　[B6O14](10-)　groups　formed　by　one　BO3　triangle　bonded　to　one　[B5O12](9-)　double　ring,　and　[B6O13](8-)　groups　consisting　of　one　BO3　triangle　linked　to　one　[B5O11](7-)　double　ring.　They　are　held　together　via　common　O　atoms　to　form　a　3D　network,　with　intersecting　open　channels　accommodating　Ba2+　cations.　The　existence　of　both　BO3　and　BO4　groups　is　confirmed　by　FT-IR　spectrum　and　an　optical　band　gap　of　3.44　eV　is　obtained　from　UV-VIS　diffuse　reflectance　spectrum.　Solid-state　fluorescence　spectrum　has　also　been　studied　exhibiting　the　maximum　emission　peak　at　around　527　nm.　Band　structure　calculations　by　the　density　functional　theory　method　indicate　that　it　is　a　direct　band-gap　insulator.