Ionic liquids have attracted much attention in the analysis of a variety of species. The functional groups in ionic liquids can result in highly efficient separation and enrichment and, because of their typical lack of volatility, they are environmentally benign. We grafted imidazole cations onto the surface of chloromethyl polystyrene, denoted PS-CH2-[MIM](+)Cl(-), and this modified polymer was used to selectively extract the protein hemoglobin (Hb). The prepared extractant PS-CH2-[MIM](+)Cl(-), containing 2 mmol immobilized imidazole groups per gram polymer, was characterized by FT-IR, surface charge analysis, and elemental analysis. The adsorption efficiency was 91%. The adsorption capacity of the PS-CH2-[MIM](+)Cl(-) for Hb was 23.6 μg mg(-1), and 80% of the retained Hb could be readily recovered by use of 0.5% (m/v) aqueous sodium dodecyl sulfate (SDS) solution as eluate. The activity of the eluted Hb was approximately 90%. The prepared imidazole-containing solid phase polymer was used for direct adsorption of Hb without use of any other solid matrix as support of the ionic liquid. The material was used in practice to isolate Hb from human whole blood.