The cyclopolymerization of 3,4-di-O-allyl-1,2 : 5,6-dianhydro-D-mannitol (1) was carried out using BF3 . OEt2 and t-BuOK. The polymer obtained by the polymerization with BF3 . OEt2 mainly consisted of (1-->6)-bonded 3,4-di-O-alkyl-2,5-anhydro-D-glucitol as the five-membered constitutional repeating unit, though it contained a small amount of other cyclic repeating units. On the other hand, during the polymerization using t-BuOK, the stereoregular polymer (1-->6)-linked 3,4-di-0-allyl-2,5-anhydro-D-glucitol (2) was synthesized via a regio-and stereoselective mechanism. Cleavage of the allyl ether linkage in polymer 2 occurred to produce the polymer consisting of only 2,5-anhydro-D-glucitol units, i.e., (1-->6)-2,5-anhydro-D-glucitol (3). Chromatographic enantioseparation of chloroquine and troger base has been performed on (3,5-dimethylphenyl)carbamate and 4-methylbenzoate derivatives of 3 as a chiral stationary phase for high-performance liquid chromatography.