The first direct enzymatic method is reported for the synthesis of cis and trans P-amino acid enantiomers through the lipase-catalyzed enantioselective hydrolysis of alicyclic beta-amino esters in organic media. High enantioselectivities (E usually > 100) were observed when the Candida antarctica lipase B catalyzed reactions were performed with H2O (0.5 equivalents) in iPr(2)O at 65 degrees C. The resolved products, obtained in good yields (>= 42%), could be easily separated.