As in previous years our chapter has been devoted mostly to the experimental spin‐spin couplings which occur either directly across chemical bonds, nJAB, or through hydrogen bonds, nhJAB and through space, TSJAB. For the first time also scalar J‐couplings mediated by van der Waals interactions have been reported. Since in the J couplings crucial information on the electron structure of a chemical bond and the structure of a compound is encoded, its knowledge provides an opportunity for creative designing of new chemical reactions leading to unknown molecular structures or elucidation of biosynthetic pathways. In many papers the experimental couplings have been confronted with their either ab initio or DFT calculated values. One section of our chapter has been devoted to residual dipolar couplings whose role in the constitutional, configurational and conformational analysis not only of large but also of small molecules is constantly increasing.