Abstract Manganese is one of the most prominent candidates for catalysis in looking for novel reactivity, owing to its less toxic, inexpensive, and earth‐abundant nature. In recent decade, manganese‐catalyzed CH functionalization of heterocycles has emerged as a powerful and efficient method in chemical synthesis. These strategies mainly involve CH addition to unsaturated substrates, cascade CH activation/cyclization, and CH alkylation/arylation, which have found great applications in the biochemistry and natural product synthesis. This section summarizes the main advancements of manganese‐catalyzed CH functionalization of heterocycles in homogeneous catalysis.