Organic azides are highly reactive, which have long established as versatile building blocks in the assembly of structurally diverse N‐containing heterocycles. The conversion of organic azides into high‐value compounds is of great importance and a subject of enormous current interest. Transition metal‐catalyzed C(sp2)−H amination/annulation of organic azides provides a powerful tool for the transformation of organic azides into a wide range of biologically important heterocyclic frameworks. In this review, we aim to summarize the recent progress on organic azides‐mediated C(sp2)−H amination/annulation for N‐heterocycle synthesis enabled by transition metal catalysts. Representative strategies are discussed in detail, including catalytic systems, reaction scopes, limitations and mechanisms.