Polycrystals of the BiFe 2 (PO 4 ) 3 compound and Bi 1 –   x Sb х Cr 2 (PO 4 ) 3 solid solution, which form a family isostructural to α-CaMg 2 (SO 4 ) 3 (sp. gr. P 6 3 / m ), have been synthesized from an aqueous solution by the salt co-precipitation method. The samples are characterized by X-ray diffraction, IR spectroscopy, differential thermal analysis, and thermogravimetry, microprobe analysis. The BiFe 2 (PO 4 ) 3 single crystals have been grown by the flux method. The structure consists of polyhedra of three types: PO 4 tetrahedra, two face-sharing FeO 6 octahedra, and BiO 6 octahedra. Isolated PO 4 tetrahedra, which share oxygen vertices with doubled FeO 6 octahedra, form a three-dimensional Fe 2 (PO 4 ) 3 3∞ framework, whose voids are occupied by bismuth atoms. Structures of the BiFe 2 (PO 4 ) 3 and NASICON types are compared.