Two novel polymers containing glucose units as the main-chain that only differ in terms of their regioregularity were synthesized to evaluate their chiral recognition abilities as chiral stationary phases (CSPs) for high performance liquid chromatography (HPLC). The regioregular polymer (poly-5) shows clear resolution ability for the racemate of cobalt (III) acetylacetonate (Co(acac)3), whereas the corresponding regioirregular polymer (poly-3) does not show any chiral recognition for Co (acac)3. The regioregular polymer main-chain seems to play an important role not only in providing an efficient interaction with the racemate but also in expressing the chiral recognition ability as a CSP for HPLC.