The facile elaboration of optically active α-sulfanyl-substituted aldehydes makes their direct preparation from unmodified aldehydes and 1-benzylsulfanyl-1,2,4-triazole particularly valuable. The substituted aldehydes are formed with excellent enantioselectivities in the presence of sterically demanding chiral pyrrolidine derivatives as organocatalysts (see scheme). R, R′ = H, alkyl, allyl, benzyl, Ph.