AbstractHydroxynitrile lyase (HNL)‐catalysed stereoselective synthesis of β‐nitro alcohols from aldehydes and nitroalkanes is considered an efficient biocatalytic approach. However, only one S‐selective HNL—Hevea brasiliensis (HbHNL)—exists that is appropriate for the synthesis of (S)‐β‐nitro alcohols from the corresponding aldehydes. Further, synthesis catalysed by HbHNL is limited by low specific activity and moderate yields. We have prepared a number of (S)‐β‐nitro alcohols, by kinetic resolution with the aid of an R‐selective HNL from Arabidopsis thaliana (AtHNL). Optimization of the reaction conditions for AtHNL‐catalysed stereoselective C−C bond cleavage of racemic 2‐nitro‐1‐phenylethanol (NPE) produced (S)‐NPE (together with benzaldehyde and nitromethane, largely from the R enantiomer) in up to 99 % ee and with 47 % conversion. This is the fastest HNL‐catalysed route known so far for the synthesis of a series of (S)‐β‐nitro alcohols. This approach widens the application of AtHNL for the synthesis not only of (R)‐ but also of (S)‐β‐nitro alcohols from the appropriate substrates. Without the need for the discovery of a new enzyme, but rather by use of a retro‐Henry approach, it was used to generate a number of (S)‐β‐nitro alcohols by taking advantage of the substrate selectivity of AtHNL.