Mixed phosphates Al1–xGaxPO4 (0.0≤ x ≤1.0), with orthorhombic structure, have been prepared by co-precipitation method followed by annealing at high temperature (T≈1350˚C) and investigated by using powder X-ray diffraction and NMR spectroscopy. A systematic decrease observed for the unit cell parameters with increasing Ga3+ contents, suggests the formation of a solid solution between AlPO4 and GaPO4.31P MAS NMR spectra of both AlPO4 and GaPO4 show a single peak at δ = –24.6 and –8.5 ppm, respectively. For mixed phosphates, multi-component 31P NMR spectra characterized by varying values of chemical shifts, have been observed due to the existence of different types of 31P structural configurations formed by varying number of Al3+ þ and Ga3+ as its next nearest neighbours. The intensity analysis of these component peaks suggested a perfectly random distribution of Al3+ and Ga3+ cations in these mixed phosphates. Chemical shift anisotropy parameters for the different structural configurations of 31P have been evaluated from the intensity analysis of the spinning side bands corresponding to different isotropic peaks.27AlNMR spectra of mixed phosphate samples exhibited a slightly asymmetric broad peak at δ ≈ 42.0 ppm, which is characteristic of the tetrahedral configuration of Al3+ ions with significant covalent bonding between the metal and oxygen ions.