Organophosphorus compounds are essential in pharmaceuticals, agrochemicals, and biologically active molecules, creating demand for precise stereochemical analysis. 31P NMR spectroscopy has become a key method for studying the structure and stereodynamics of phosphorus-containing systems due to the favorable properties of the 31P nucleus, including high natural abundance, spin-½ characteristics, and a broad chemical shift range. In addition to structural assignment, 31P NMR enables connectivity analysis through heteronuclear couplings and supports conformational studies using scalar coupling relationships. These capabilities are particularly valuable in complex systems such as ProTide prodrugs, where stereochemistry influences biological function. This chapter highlights the application of 31P NMR in chiral recognition, demonstrating its sensitivity to electronic environment and stereochemical variation, and establishing it as a reliable tool in synthetic, medicinal, and bioinorganic chemistry.