Thiamine (VB1) has been proved to be a powerful biocatalyst for various organic transformations. VB1 offers several unique advantages, such as economical, non‐toxic, stable and water soluble. Excellent outcomes have been achieved in synthetic applications using VB1 as a catalyst. This review summarizes recent developments in the field of VB1 biocatalysis, allowing the construction of various biologically active heterocyclic scaffolds.