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C−N bonds are widely found in natural products, medicinal molecules and multifunctional materials. In recent years, the construction of C−N bonds through a radical coupling reaction between carbon‐centered radicals with nitrogen‐centered radicals has emerged as a frontier area in organic chemistry. This review summarizes the recent advances (especially those after 2012) in radical coupling reactions that facilitate the formation of C−N bonds. The main achievements on this area are presented according to the pattern of the nitrogen‐centered radicals generated. Selected examples of substrates are listed and special attention is paid to the reaction mechanisms. Moreover, a personal outlook is described at the end.