AbstractThe racemization mechanism of tert‐butylphenylphosphido‐borane is investigated experimentally and theoretically. Based on this converging approach, it is shown, first, that several phosphido‐borane molecular species coexist at the time of the reaction and, second, that one particular of both initially assumed reactive routes most significantly contribute to the overall racemization process. From our converging modeling and experimental measurement, it comes out that the most probable species to be here encountered is a phosphido‐borane‐Li (THF)₂ neutral solvate, whose P‐stereogenic center monomolecular inversion through a Y‐shaped transition structure (Δ_rG°^≠: 81 kJ mol⁻¹) brings the largest contribution to the racemization process.