[superscript 31]P{[superscript 1]H} nuclear magnetic resonance spectroscopy is a particularly useful tool for studying the reactions of P-donor ligands such as phosphines and phosphites with transition metals and other Lewis bases because the reactions take place on the nonbonding pair of electrons on the phosphorus. In addition, [superscript 31]P has a 100% natural abundance and a high gyromagnetic ratio resulting in a high sensitivity that allows the spectra to be recorded using small amounts of sample. An activity that combines air-sensitive synthesis of transition metal complexes of P-donor ligands and the characterization of these complexes with [superscript 31]P{[superscript 1]H} NMR spectroscopy has been developed for an upper-division, laboratory-based inorganic course. This laboratory familiarizes students with this useful nucleus for NMR spectroscopy and allows them to study the factors that affect the [superscript 31]P{[superscript 1]H} NMR chemical shifts of phosphorus-donor ligands and their transition metal complexes. Details of the activity, including procedure and pretest, are provided. Alternative methods and presentations are also proposed.