The first catalytic enantioselective beta-hydroxylation of alpha,beta-unsaturated aldehydes is presented. Using commercially available (E)-benzaldehyde oxime in the presence of 2-[bis(3,5-bis-trifluoromethyl-phenyl)trimethyl-silanyloxymethyl]pyrroli dine as organocatalyst, the corresponding chiral carbonyl beta-oxime ethers are obtained in high yields and with excellent enantioselectivities. These optically active carbonyl and hydroxy beta-oxime ethers are highly interesting biological compounds in, e.g., sex pheromone analogues, highly potent antiinflammatory agents, and penicillin and cephalosporin analogues. The chiral carbonyl beta-oxime ethers can be reduced to the corresponding 1,3-diols in high yields. Furthermore, the organocatalytic enantioselective beta-hydroxylation of alpha,beta-unsaturated aldehydes could be performed on gram scale without loss of enantioselectivity.