Due to the growing significance of sustainable and environmentally friendly organic transformations, there has been increasing interest in utilizing vitamins as catalysts owing to their green nature, biocompatibility, and ease of preparation. Among these, Vitamin B1, also known as thiamine stands out for its nonflammable, water‐soluble, inexpensive, and non‐toxic characteristics. This review summarized recent developments on the catalytic application of Vitamin B1 in organic transformations, particularly in facilitating C‐C and C‐X (N, O, S) bond formations, thus demonstrating its efficacy in synthesizing complex molecules. Vitamin B1 exhibits versatility in these reactions, functioning as both an organocatalyst as well as a co‐catalyst or ligand with other metal catalysts. The review also delves into the application of thiamine diphosphate ‐dependent enzymes as catalysts in organic reactions, drawing inspiration from natural enzymatic processes. Additionally, the mechanistic intricacies of thiamine‐catalyzed reactions and the roles of co‐catalysts or additives are thoroughly examined, providing insights into reaction pathways and facilitating informed catalyst design strategies.