The radical polymerization of methyl n-octadecyl itaconate initiated with AIBN, produces poly(methyl n-octadecyl itaconate) with a yield of 47% and a molecular weight of about 10(5) g/mol. C-13-NMR studies point out that this polymer is mainly syndiotactic. The combined studies of DSC and solid state C-13 CP/MAS NMR indicate that the polymer side chains are able to crystallize in a paraffinic phase, presumably in an hexagonal form which melts at 44degreesC with a DeltaH of 4.8Kcal/mol.