Enantiopure 1,2‐diols are widely used in the production of pharmaceuticals, cosmetics, and functional materials as essential building blocks or bioactive compounds. Nevertheless, developing a mild, efficient and environmentally friendly biocatalytic route for manufacturing enantiopure 1,2‐diols from simple substrate remains a challenge. Here, we designed and realized a step‐wise biocatalytic cascade to access chiral 1,2‐diols starting from aromatic aldehyde and formaldehyde enabled by a newly mined benzaldehyde lyase from Sphingobium sp. combined with a pair of tailored‐made short‐chain dehydrogenase/reductase from Pseudomonas monteilii (PmSDR‐MuR and PmSDR‐MuS) capable of producing (R)‐ and (S)‐1‐phenylethane‐1,2‐diol with 99% ee. The planned biocatalytic cascade could synthesize a series of enantiopure 1,2‐diols with a broad scope (16 samples), excellent conversions (94%–99%), and outstanding enantioselectivity (up to 99% ee), making it an effective technique for producing chiral 1,2‐diols in a more environmentally friendly and sustainable manner.