A number of lead(II) O,O′-dialkyldithiophosphate complexes were studied by 13C, 31P, and 207Pb MAS NMR. Simulations of 31P chemical shift anisotropy using spinning sideband analysis reveal a linear relationship between the SPS bond angle and the principal values δ22 and δ33 of the 31P chemical shift tensor. The 31P CSA data were used to assign ligands with different structural functions. In the cases of Adiethyldithiophosphate and di-iso-butyldithiophosphate lead(II) complexes, 2J (31P, 207Pb)-couplings were resolved and used to confirm the suggested assignment of the ligands. The SIMPSON computer program was used to calculate 31P and 207Pb spectral sideband patterns.