Copolymerization of MAn and CHDDVE was conducted by using azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) as the initiator, ethyl acetate (EA) or n-butyl acetate (BA) as the solvent, and n-hexane as the precipitator. Effects of several factors on monomer conversion were studied, such as reaction time, reaction temperature, composition of the monomer feed (MAn/CHDDVE) and initiator concentration. Molecular weight and its polydispersity and polymer material morphology were characterized by gel permeation chromatography (GPC) and transmission electron microscope (TEM) technologies, respectively. It was demonstrated that CTC was formed in MAn/CHDDVE system, based on ultraviolet-visible spectroscopy (UV-vis) analysis. The product was alternating copolymer with high crosslinking degree, so it could not be dissolved in common solvents, e.g. water, chloroform, N, N-dimethyl formamide (DMF), tetrahydrofuran (THF) and acetone (Ac).