Аннотация:The new oxophosphates: [O2Bi3]O(PO4) (I), Ni(BiO)2(PO4)(OH) (II) and KBi4{Ni2O4(PO4)3} (III) were synthesized by a hydrothermal method in the Bi(OH)3–NiCO3– K2CO3–K3PO4 system (T = 690-700К, P = 480-500 atm) and studied by single-crystal X-ray diffraction. The structures of the oxophosphates were refined in the anisotropic approximation of the atomic displacement parameters to final R1 = 0.0410(I), 0.0409(II), 0.0576(III). The comparative crystal chemical analysis of a series of fluorite-like bismuth oxophosphates is confirmed that the new bismuth oxophosphate (I) is the phase derivative from [O4Bi5]О0.5(PO4)2 with ionic conductive properties. The namibite type structure of nickel, bismuth oxophosphate (II) contains infinite chains {Ni(OH)(PO4)}∞ built of corner-sharing NiO6 octahedra. The new layer potassium, bismuth, nickel oxophosphate (III) is expected to be paramagnetic with very weak antiferromagnetic exchange interactions.