In this chapter, which is devoted to applications of spin–spin couplings, the literature published between June 2012 and May 2013 has been reviewed. The data included has been arranged according to (i) the increasing atomic number of the nuclei involved, and (ii) the number of the bonds separating them. The spectrum of the studied compounds in which scalar spin–spin couplings have been applied is quite impressive. It starts from the HD molecule via small organic compounds, organometallic complexes and minerals up to very large and complex biological systems. In a number of the reviewed papers measurements of the couplings between quadrupolar nuclei have been reported. One section of this chapter covers the papers devoted to residual dipolar couplings whose role in the constitutional, configurational and conformational analysis of not only large biological systems but also small organic molecules is constantly increasing. In many papers experimental data has been combined with theoretical calculations, which allowed the authors to gain a deeper insight into the electron distribution within a given chemical bond and significantly facilitated the conformational analysis of the studied compounds.