It is demonstrated on a polycrystalline powder sample of Cd-3(PO4)(2), given a known single-crystal X-ray structure, that two-dimensional P-31 double-quantum single-quantum MAS correlation experiments allow unique assignment of multiple P-31 resonances to specific P sites in the structure of such inorganic orthophosphates. The eigenvalues of the P-31 and Cd-113 shielding tensors of Cd-3(PO4)(2) are reported, the determination of which requires usage of a 2D MAS spinning sideband separation experiment.