Iron-catalyzed oxidative coupling between two C-H bonds, and C-H with heteroatom-H bonds have received significant attention due to its atom-economy, and sustainable nature. Oxidative coupling and annulations strategy provide step-economy route towards the synthesis of heterocycles. This review highlights the Fe-catalyzed C-C and C-heteroatom oxidative coupling reactions and its potential application in the synthesis of heterocycles, bioactive natural products.