Random and block copolymers containing styrene and mono n-alkyl itaconates with n= 12, 14, 16, 18 and 22 have been prepared by free radical polymerization and nitroxide-mediated radical polymerization. The molar fraction of the mono n-alkyl itaconate in block copolymers increased with increasing size of the alkyl group in the ester substituent. A calorimetric study of all these copolymers was performed. No glass transition (Tg) was observed in the temperature range -30ºC-120ºC for random copolymers. Melting process attributed to crystalline order in the long side chains was observed for some copolymers depending on their composition and of the monoitaconate chain side length.