A number of isostructural double phosphates of NASICON type in the Na2O-P2O5-Fe2O3- Nb2O5 system were prepared by solid-phase synthesis. The lattice parameters of the resulting compounds were calculated based on the data of X-ray powder diffraction. The process of partial reduction of Nb5+ to Nb4+ was determined by ESR and diffuse reflection spectroscopy at specified ratios of components.