1-(triethyl four amine) ethyl-3-methyl chloride ionic liquid ([N4MIM]Cl) was prepared on the base of N-methylimidazole by 1,2-dichloroethane to obtain the intermediates 1-chloro-ethyl-3-methyl chloride ionic liquid ([CeMIM]Cl) and then reacting with triethylene tetramine. The chemical structure of [N4MIM]Cl was confirmed by FT-IR and 1HNMR. [N4MIM]Cl possessed a lower REDOX potential through cyclic voltammetry (CV) measurement, E1,2 -0.472V. [N4MIM]Cl presented a perfect coordination property compared with organic ligands. The obtained ionic liquid [N4MIM]Cl coordinated with CuBr was used to catalyze atom transfer radical polymerization (ATRP) of methyl爉ethacrylate (MMA) in 1-allyl-3-methylimidazolium chloride ([AMIM]Cl) and it indicated by gel permeation chromatography (GPC) that the coordination ionic liquid [N4MIM]Cl presented the perfect controllability to the ATRP reactions. The residues of Cu2 in polymerization product polymethyl methacrylate (PMMA) was only 360 mg穔g-1 by atomic absorption spectrometry (AAS) determination. It showed that [N4MIM]Cl was conducive to the separation of catalyst from the obtained product compared with the traditional organic ligands.