A straightforward synthesis of phosphaisocoumarins is achieved by the rhodium-catalyzed oxidative coupling of diarylphosphinic and phenylphosphonic acid derivatives with alkynes. The P鈥揙H groups effectively act as the key function for the regioselective C鈥揌 bond cleavage. Related oxidative coupling of phenylphosphine oxides with alkenes can also be conducted smoothly under similar conditions.