Rotational echo double resonance (REDOR) of spin- nuclei is an extremely useful tool for the determination of distances in solids as well as of relative orientations of chemical shift and dipole tensors. We present the corresponding version for measuring the relative orientation of electric quadrupole and dipole tensors and demonstrate its applicability for non-bridging oxygens in phosphate glasses using 17O–{31P} REDOR NMR. The orientational information is found in the changes of the second-order quadrupole patterns as a function of the echo delay. Results and numeric simulations are presented for 17O–{31P} REDOR NMR of 17O-enriched sodium phosphate glasses. For non-bridging oxygens, the symmetric quadrupole tensor is found to be aligned along the phosphorus–oxygen bond. The distance between P and the non-bridging oxygen is calculated for two glasses of different compositions.