Poly(benzyl methacrylate) (PBzMA) and its copolymers exhibit lower critical solution temperature (LCST)-type phase separation in common hydrophobic ionic liquids (ILs) such as 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfone)imide ([C(2)mim][NTf2]). The turbidity measurements for PBzMA/IL mixed systems reveal that the LCST-type phase separation temperatures change significantly with the changes in the chemical structures of polymers and ILs. Moreover, cross-linked PBzMA gels show reversible and discontinuous volume phase transition in [C(2)mim][NTf2] with the changes in temperature.