The convenient and atom-economical synthesis of substituted bicyclic pyridylphosphonates was achieved by the cationic Rh(I)/H8-binap-complex-catalyzed [2+2+2] cycloaddn. of 1,6- and 1,7-diynes with di-Et phosphorocyanidate. These reactions may proceed via an azarhodacyclopentadiene intermediate in addn. to the rhodacyclopentadiene intermediate. [on SciFinder(R)]