Phosphorus-carbon spin-spin coupling constants in a series of salient heterocyclic phosphines were calculated at the SOPPA(MP2) level including evaluation of relativistic and solvent effects. A number of the locally dense basis set schemes were thoroughly investigated in terms of their accuracy versus computational demands. The most effective computational scheme was tested in a benchmark series to provide a very good correlation between (2)J(PC) calculated at the SOPPA(MP2) level and experiment. A marked dihedral angle dependence of (2)J(PC) was demonstrated, and this could be used in stereochemical studies of a wide series of organophosphorus compounds based on the phosphorus-carbon coupling constants.