Аннотация:Two novel bismuth oxosalts, β-Bi3O3(VO4) and KBi5O5(PO4)2, synthesized hydrothermally crystallize in the triclinic space group P-1 with a = 5.7337 (6), b = 7.1029 (8), c = 9.298 (1) Å, α = 80.334 (3), β = 78.576 (3), γ = 68.557°(3), V = 343.58 (7) Å3, Z = 8 and in the monoclinic, P21/c sp.gr. with a = 8.0264 (6), b = 5.4616 (4), c = 27.769 (2), β = 95.697 (2), V = 1211.29 (16) Å3, Z = 4, respectively. Their crystal structures are built on corrugated layers formed of the linkage of oxo-centered OBi4 or OBi4, OBi5 and O(Bi,K)4 tetrahedra sharing edges and surrounded by isolated vanadate/phosphate groups. β-Bi3O3(VO4) are suggested to be the high-pressure polymorph with more symmetrically crystal structure than the α-modification; this agrees with the trend of decreasing structural complexity with increasing pressure. The optical properties of β-Bi3O3(VO4) and KBi5O5(PO4)2 were investigated. The first one exhibits a weak emission at room temperature in the red-near-infrared region with maximum at 650-660 nm, whereas the second bismuth oxosalt emits in the green orange range with peak at 550 nm.