An enantioconvergent biotransformation of racemic styrene oxide by using two recombinant microbial epoxide hydrolases (EHs) in one pot has been investigated to prepare enantiopure vicinal diols. The recombinant whole cell possessing EH gene from Aspergillus niger LK or Rhodotorula glutinis exhibited a complementary enantioselectivity and regioselectivity, compared to the recombinant cell containing Caulobacter crescentus EH gene. When two recombinant microbial EHs were used in combination, 1.3 g of enantiopure (R)-1,2-phenylethandiol with more than 90% enantiopurity and 95% overall yield was obtained from 1.2 g of racemic styrene oxide in a preparative-scale batch enantioconvergent biotransformation.