One- and two-dimensional refocused MAS-J-INEPT NMR experiments in the solid state (through-bond polarization transfer) involving the highly abundant 31P spin and the rare 29Si spin are described for the crystalline silicophosphate phase Si5O(PO4)6 and complex mixtures of SiP2O7 polymorphs. The evaluation of the 2JP-O-Si coupling constants for all 29Si sites is obtained by the careful analysis of the INEPT build-up curves under fast MAS. The results are in agreement with the crystallographic data, taking into account the various J coupling paths. The efficiency of the experiment is demonstrated by its application to more complex systems such as silicophosphate amorphous gels (obtained by the sol−gel process).