A series of comb like poly(p-n-alkylstyrene)s with linear alkyl groups, containing even numbers of carbon atoms from 12 up to 22 were synthesized by radical polymerization and characterized by FTIR, H-1 NMR, TGA, TVA DSC, and WAXS. All polymers were obtained in good yields and were soluble in organic solvents as chloroform, dichloromethane or tetrahydrofuran and insoluble in methanol; they are stable up to temperatures near 300 A degrees C. On the other hand, the alkylic side chains of all series are able to crystallize in a paraffinic phase in which the melting temperature and enthalpy increase with the methylene number of the n-alkyl chain.