Mengke Peng, Kaiqiang Jing, Guoqiang Ma, Youan Ji, Aibing Chen
ABSTRACT Saccharide additives have recently emerged as a green, low‐cost, and highly efficient strategy to stabilize Zn metal anodes. Previously reported monosaccharides, disaccharides, oligosaccharides, polysaccharides and their derivatives can effectively suppress dendrite growth, prolong cycle life, and push Coulombic efficiency beyond 99.0%. However, most investigations focus on a single saccharide and its specific mechanism, lacking a systematic review and horizontal comparison of the relationship between the molecular structure and regulatory mechanism, which limits the rational design and performance optimization of saccharide additives. This review comprehensively summarizes and deeply analyzes the common principles by which saccharide additives regulate Zn 2+ solvation, suppress hydrogen evolution, construct water‐poor interface layers, optimize interfacial electric field, and induce oriented Zn 2+ deposition. This review elucidates the structure‐function relationships across different categories of saccharide additives. The abundant oxygen‐containing functional groups, steric hindrance effects, and chain length of saccharide additives act synergistically to deliver a “desolvation‐confinement‐orientation” triple function. This review further proposes forward‐looking strategies for molecular engineering and multi‐component synergy to address existing challenges, and aims to provide critical insights for the design and optimization of long‐lasting zinc‐based energy storage systems.