Carboxylic acids and their derivatives are ubiquitous compounds in organic chemistry, and are widely commercially available in a large structural variety. Recently, carboxylic acids have been frequently used as non-toxic and environmentally benign alternatives to traditional organohalide coupling partners in various carbon–carbon and carbon–heteroatom cross-coupling reactions. Along this line, several methods have been reported for the synthesis of nitrogen-containing organic compounds through decarboxylative cross-coupling reactions between carboxylic acids and N–H compounds. This review focuses on recent advances and discoveries on these reactions with special attention on the mechanistic aspects of the reactions.