Enantiopure (R)-and (S)-2-phenylglycinols are important chiral building blocks for pharmaceutical manufacturing. Several chemical and enzymatic methods for their synthesis were reported, either involving multi-step synthesis or starting from a relatively complex chemical. Here, we developed one-pot simple syntheses of enantiopure (R)-and (S)-2-phenylglycinols from cheap starting materials and renewable feedstocks. Enzyme cascades consisting of epoxidation-hydrolysis-oxidation-transamination were developed to convert styrene 2 a to (R)-and (S)-2-phenylglycinol 1 a, with butanediol dehydrogenase for alcohol oxidation as well as BmTA and NfTA for (R)-and (S)-enantioselective transamination, respectively. The engineered E. coli strains expressing the cascades produced 1015 mg/L (R)-1 a in > 99% ee and 315 mg/L (S)-1 a in 91% ee, respectively, from styrene 2 a. The same cascade also converted substituted styrenes 2 b-k and indene 2 l into substituted (R)-phenylglycinols 1 b-k and (1R, 2R)-1-amino-2-indanol 1 l in 95-> 99% ee. To transform biobased L-phenylalanine 6 to (R)-1 a and (S)-1 a, (R)-and (S)-enantioselective enzyme cascades for deaminationdecarboxylation-epoxidation-hydrolysis-oxidation-transamination were developed. The engineered E. coli strains produced (R)-1 a and (S)-1 a in high ee at 576 mg/L and 356 mg/L, respectively, from L-phenylalanine 6, as the first synthesis of these compounds from a bio-based chemical. Finally, L-phenylalanine biosynthesis pathway was combined with (R)-or (S)-enantioselective cascade in one strain or coupled strains, to achieve the first synthesis of (R)-1 a and (S)-1 a from a renewable feedstock. The coupled strain approach enhanced the production, affording 274 and 384 mg/L (R)-1 a and 274 and 301 mg/L (S)-1 a, from glucose and glycerol, respectively. The developed methods could be potentially useful to produce these high-value chemicals from cheap starting materials and renewable feedstocks in a green and sustainable manner.