Highly functionalized polyol building blocks have been synthesized by means of stereoselective chemoenzymatic C–C bond formation followed by stereoselective reduction. Catalysis by thiamine diphosphate (ThDP) dependent benzaldehyde lyase (BAL) with glyceraldehyde acetonide as acceptor substrate gave highly stereoenriched polyols such as (1S,2S,3R)‐1‐phenylbutane‐1,2,3,4‐tetrol (1), the 3,4‐protected anti‐1,2‐diol 5, and the precursor of both compounds, 2‐hydroxyketone 4.