A kinetics investigation of the interchangeable process in the equilibrium between the Z‐ and E‐isomers of a stable phosphorus ylide involving a 2‐mercaptobenzoxazol has been undertaken by the variable temperature 1H‐NMR technique. Activation parameters such as k−1, k1, ktotal, Ea1, Ea‐1, Eatotal, ΔS#, ΔH#, and ΔG# along with thermodynamic parameters alike Ke, ΔH°, ΔG°, and ΔS° were obtained from experimental data for the forward and reverse steps of opposing reaction. © 2013 Wiley Periodicals, Inc. Concepts Magn Reson Part A 42A: 101–107, 2013.