Crystallographic structures of the three NaSbR(PO 4 ) 3 (R = Cr, Fe, In) phases were determined at room temperature from X-ray powder diffraction (XRD) data using the Rietveld analysis. The three compounds belong to the Nasicon structural family. The presence of the (303) reflection in all XRD spectra of NaSbR(PO 4 ) 3 shows clearly that all compounds crystallise in rhombohedral system with R 3 space group. Na atoms are practically ordered within the two positions, 3a and 3b, of M1 sites. Structure refinements show also a partially-ordered distribution of Sb 5+ and R 3+ ions within the Nasicon framework. A Raman and Infrared spectroscopic study was used to obtain further structural information about the nature of bonding in NaSbR(PO 4 ) 3 (R = Cr, Fe, In) phases.