A series of novel N,O-type chiral Iigands derived from enantiopure inherently chiral calix[4]arenes containing quinolin-2-yl-methanol moiety in the cone or partial-cone conformation have been synthe-sized and characterized. Moreover, they have been applied to the catalytic asymmetric addition of di-ethylzinc to benzaldehyde, which represents the first example that the inherently chiral calixarene can be used as the chiral ligands for the catalytic asymmetric synthesis.