An enantioselective synthesis of a new class of benzophosphole-based heterocycles bearing a fused triazole ring with enantioselectivities up to 99% is reported. The key steps of the synthesis are based on an innovative stereospecific phosphinyl N→O migration of aminophosphine-boranes into phosphinites, followed by an intramolecular cyclization. Five X-ray structures of P-chirogenic benzotriazolophospholes and gold(I) complex were established, for assigning absolute configurations, stereochemistry of reactions and the placement of the triazole substituent in syn-position of the P-center.