Intramolecular C−H insertion into the methyl group of the amino substituent of 1 is shown by density functional theory calculations to stabilize this intermediate in the formation of the novel 1:1 carbene–phosphaalkyne adduct 2. Compound 2 is formed in near quantitative yield by reaction of 1,3,4,5‐tetramethylimidazol‐2‐ylidene with P≡CNiPr2.