ABSTRACT Vanadium (V)‐based materials have emerged as a distinctive and versatile class of sulfur electrocatalysts for high‐performance lithium–sulfur (Li─S) batteries. Their flexible valence states, strong chemical polarity, and tunable local structures enable robust polysulfide adsorption and accelerated sulfur redox kinetics. This review provides a systematic overview of V‐based electrocatalysts, including oxides, sulfides, nitrides, carbides, borides, metal–organic frameworks, and single‐atom configurations, and establishes activity‐structure relationships that link their electronic structures, coordination chemistry, and surface properties to catalytic function. Key strategies for performance regulation, such as heteroatom modulation, defect engineering, ligand‐filed manipulation, and hybridization with conductive hosts, are summarized to elucidate effective design principles for enhancing intrinsic and practical catalytic activity. Furthermore, remaining challenges and future research directions are outlined, highlighting the opportunities in atomic‐level material designs, mechanistic elucidation, and device‐level optimizations under practical conditions. Collectively, these insights are expected to advance V‐based sulfur electrocatalysis toward practically viable Li─S battery technology and inspire broader innovations in next‐generation energy storage and conversion systems.
Li et al. (Mon,) studied this question.