A versatile synthesis of α-amino bisphosphonates has been achieved through one-pot interrupted Ritter-type reaction under mild conditions. The reactive Ritter intermediate nitrilium is in situ generated by treatment of nitrile with readily accessible Tf2O/HC(OR1)3, which is trapped by phosphite ester to deliver the desired product. This protocol is efficient, scalable, and well compatible with a broad scope of substrates. In addition, plentiful characteristic JP-C couplings including unusual five-bond long-range 5JP-C and 3JP-C across quaternary carbon and hetero (N) atoms were observed in 13C NMR spectra.