The　first　examples　of　bismuth　fluoride　selenites　with　d0-TM/TeVI　polyhedrons,　namely,　Bi4TiO2F4(SeO3)4　(1),　Bi4NbO3F3(SeO3)4　(2),　Bi4TeO4F2(TeO3)2(SeO3)2　(3),　Bi2F2(MoO4)(SeO3)　(4)　and　Bi2ZrO2F2(SeO3)2　(5)　have　been　successfully　synthesized　under　hydrothermal　reactions　by　aliovalent　substitution.　The　five　new　compounds　feature　three　different　types　of　structures.　Compounds　1–3,　containing　TiIV,　NbV　and　TeVI　respectively,　are　isostructural,　exhibiting　a　new　3D　framework　composed　of　a　3D　bismuth　oxyfluoride　architecture,　with　intersecting　tunnels　occupied　by　d0-TM/TeVI　octahedrons　and　selenite/tellurite　groups.　Interestingly,　compound　Bi4TeO4F2(TeO3)2(SeO3)2　(3)　is　the　first　structure　containing　SeIV　and　mixed-valent　TeIV/TeVI　cations　simultaneously.　Compound　4　features　a　new　3D　structure　formed　by　a　3D　bismuth　oxyfluoride　network　with　MoO4　tetrahedrons　and　selenites　groups　imbedded　in　the　1D　tunnels.　Compound　5　displays　a　novel　pillar-layered　3D　open　framework,　consisting　of　2D　bismuth　oxide　layers　bridged　by　the　[ZrO2F2(SeO3)2]6−　polyanions.　Theoretical　calculations　revealed　that　the　five　compounds　displayed　very　strong　birefringence.　The　birefringence　values　of　compounds　1–3,　especially,　are　above　0.19　at　1064　nm,　which　are　larger　than　the　mineral　calcite.　Based　on　the　structure　and　property　analysis,　it　was　found　that　the　asymmetric　SeO3　groups　(and　TeO3　in　compound　3)　displayed　the　largest　anisotropy,　compared　with　the　bismuth　cations　and　the　d0-TM/Te　polyhedra,　which　is　beneficial　to　the　birefringence.　©　2019　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim