Two new chiral ionic liquids, 1-((-)-menthoxycarbonylmethylene)-3-methylimidazolium hexafluorophosphate and l-((-)-menthoxycarbonylmethylene)-3-hexadecylimidazolium hexafluorophosphate, were designed and prepared. Their chemical structures were characterized by 1H-NMR. Reverse atom transfer radical polymerization of methyl methacrylate(MMA) in these two ionic liquids was carried out using AIBN/CuC12/bipy as the initiating system. The resultant well-defined polymethyl methacrylate (PMMA) was employed as a macroinitiator to induce the atom transfer radical polymerization of menthyl methacrylate (MnMA) in chlorobenzene, which yielded a PMMA-b-PMnMA diblock copolymer with narrow polydispersity.