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The azido group is found in large numbers of natural products, drugs, biochemicals and materials and to date, many elegant and useful methods for the synthesis of organic azides and their transformations have been documented. In this review, we provide a summary of the state of the art of radical azidation for the construction of C(sp3)-N3 bonds. There is a specific emphasis on the synthetic reactions involving C(sp3)-H azidation, decarboxylative azidation and difunctionalized azidation of olefins. This review will be useful to those working in this field and hopefully could inspire further development of radical azidation reactions.