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.　©　2024　Wiley　Periodicals　LLC.