Aromatic epoxides 1a and 1b provided both enantiomers of diols with excellent conversions and high enantioselectivities. Epoxide 1c with a benzyl group led to optically active diols up to 88.7:11.3 er and a good conversion of 74%. Epoxides bearing an ether function, derivatives of glycidol, gave moderate conversions except 1d, but reached high enantioselectivity up to 94:6 er. Interestingly, the ring opening of racemic epoxides 1g furnished both enantiomers 2g of mephenesin, a muscle relaxant.