1,3-Dipolar cycloaddition reaction between organic azide and metal carbyne is a useful strategy to con-struct metallacycles.However,the electronic behavior of organic azide in 1,3-dipolar cycloaddition reactions is less explored.This work revealed the unexpected role of organic azide as electrophiles in its cycloadditions with various metal carbynes.The feasibility and regioselectivity of a Fischer-type osmium carbyne in its reaction with an organic azide are explained by the increased nucleophilicity of carbyne carbon upon bending.