Optical resolution by liquid chromatography, particularly by high-performance liquid chromatography, has become a useful and important method for resolving enantiomers. In this review, the author discusses mainly the optical resolution by liquid chromatography with chiral polymers. The polymers include proteins, cellulose and other polysaccharide derivatives, cross-linked polymers with chiral cavity, optically active polyacrylamides, and poly (triphenylmethyl methacrylate). Chiral discrimination ability of the polymers depends very much on their second or higher order structure. Mostly, a higher chiral recognition ability is attained when the polymer exist as an order structure. This is a pronounced difference between the polymeric stationary phases and the stationary phases consisting of silica gel and chiral small molecules.