As an important class of nitrogen-containing functional molecules, azides have attracted considerable attention in synthetic chemistry and functional materials due to their reaction diversity and derivatization capability. Azide-based difunctionalization of alkenes, as a pivotal research direction in this field, holds significant implications for expanding the application scope of azide compounds through research progress and mechanistic innovations. This review focuses on reaction mechanisms to systematically summarize recent advances in azide-based difunctionalization of alkenes, while outlining its application prospects in synthetic methodology and interdisciplinary fields. The incorporation of azide groups into alkene difunctionalization systems has revealed distinctive advantages for constructing nitrogen-enriched molecular architectures. This review systematically analyzes reaction mechanisms as the central framework to comprehensively summarize recent methodological advancements in alkene azide-based difunctionalization.