A polymerizable ionic liquid, N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI), was polymerized via copper-mediated atom transfer radical polymerization (ATRP). The polymerization proceeded in a living manner producing well-defined poly(DEMM-TFSI) of target molecular weight up to about 400 K (including a polycation and an counter anion). The accurate molecular weight as determined by a GPC analysis combined with a light scattering measurement, and the molecular weight values obtained exhibited good agreement with the theoretical values calculated from the initial molar ratio of DEMM-TFSI and the monomer conversion. Surface-initiated ATRP on the surface of monodisperse silica particles (SiPs) with various diameters was successfully performed, producing SiPs grafted with well-defined poly(DEMM-TFSI) with a graft density as high as 0.15 chains/nm 2 . Since the composite film made from the silica-particle-decorated polymer brush and ionic liquid shows a relatively high ionic conductivity, we have evaluated the relationship between the grafted brush chain length and the ionic conductivity.

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