The optical resolution property of 2,3,4-Tris-O-(3,5-dimethylphenylcarbamoyl)-(1-->6)-alpha-D-glucopyranan (5) toward racemic compounds has been studied as the chiral stationary phase (CSP) in high-performance liquid chromatography (HPLC). For the synthesis of (1-->6)-alpha-D-glucopyranan (4), the ring-opening polymerization of 1,6-anhydro-2,3,4-tri-O-allyl-beta-D-glucopyranose (1) has been proceeded through the stereoselective ring-opening mechanism to yield the 2,3,4-tri-O-allyl-(1-->6)-alpha-D-glucopyranan (2). For chromatographic enantioseparation of ten racemates, such as tröger's base and benzoin, using 5 as a CSP, it was found that the chiral discrimination ability of 5 with the high molecular weight polymer (CSP-5a) was higher than that with the low molecular weight polymer (CSP-5b). In addition, the elution tendency of racemates using CSP-5a was essentially identical with the results of enantioseparation using dextran tris(3,5-dimethylphenylcarbamate).