Triple phosphates A2FeTi(PO4)3 (A = Na, Rb) were synthesized by the solid-phase method and studied by electronic microscopy, electron probe X-ray microanalysis, and IR and Mossbauer spectroscopy. The crystal structure of the obtained compounds was refined by X-ray powder diffraction (the Rietveld method). The unit-cell parameters are as follows: for Na2FeTi(PO4)3 (space group R $$ \overline 3 $$ c, Z = 6), a = 8.6015(1) A, c = 21.718(1) A, V = 1391.52(1) A3; for Rb2FeTi(PO4)3 (space group P213, Z = 4), a = 9.8892(2) A, V = 967.12(1) A3. The base of the crystal structures is a mixed octahedral-tetrahedral framework {[FeTi(PO4)3]2−}3∞. Na+ and Rb+ cations are arranged in cavities of the framework. The influence of cationic substitutions on the change of the structural type of the isoformular compounds A2FeTi(PO4)3 (A = Na, Rb) was considered.