A series of racemic methyl phosphonyl-and phosphorylacetates were hydrolyzed in the presence of porcine liver esterase (PLE) under kinetic resolution conditions to give the corresponding P-chiral phosphonyl-and phosphorylacetic acids and recovered esters in moderate to high enantiomeric purity (up to 95% ee). The Jones PLE active site model was applied to explain the enantioselectivity of this reaction.