Sugar-substituted epoxides 5−8 were synthesized by asymmetric epoxidation (in CH2Cl2/water) of α-olefins having neighboring sugars (1−4) by use of an achiral oxidant (MCPBA), in which the sugar moiety acted as a chiral template. The diastereoselectivities depend on the methylene spacer between vinyl group and carbohydrate derivatives. The methylene spacer between sugar and vinyl groups influenced the diastereoselectvity. In the case of epoxidation of 4 at 27 °C for 24 h, the diastereoselectivity was the highest (99/1). Copolymerizations of 5−8 with succinic anhydride were attained at 100 °C for 72 h to give poly(ethylene succinate) having pendant carbohydrate [poly(SAn-alt-5), Mn = 1.4 × 103; poly(SAn-alt-6), Mn = 2.2 × 103; poly(SAn-alt-7), Mn = 2.9 × 103; poly(SAn-alt-8), Mn = 1.8 × 103]. The methylene spacer between sugar and epoxide has an effect on the reactivity of epoxide in copolymerization as well as the diastereoselectivity. Alternating copolymerization of 7 and glutaric anhydride gave a polyester of Mn 4.2 × 103.