Guihua Liu, Shunyao Tang, Guo Tang, Lei Gong, Qianyi Zhao, Yu‐Mei Lin
ABSTRACT Manganese‐based photocatalysis has emerged as a sustainable strategy in modern organic synthesis, leveraging manganese's natural abundance, low toxicity, versatile redox behavior, and tunable coordination environments. This review classifies manganese photocatalysts into three main structural categories: (i) dinuclear Mn 2 (CO) 10 , (ii) mononuclear complexes with simple ligands (including manganese salts), and (iii) well‐defined complexes supported by elaborate ligand frameworks. The article systematically summarizes their applications in a range of photocatalytic transformations, such as C─H functionalization, alkene modification, coupling reactions, and redox processes, along with relevant mechanistic insights and structure–activity relationships. While challenges remain in catalyst stability, structural diversity, and stereocontrol, manganese‐based photocatalysis shows strong potential for enabling greener and more sustainable synthetic routes. By providing a clear, categorization‐based overview, this review aims to encourage further developments in this rapidly evolving field.