A series of silica-supported polymeric ionic liquid (PIL)-based stationary phases derived from a vinylic L -valine ionic liquid monomer and divinylbenzene (DVB) as the crosslinking agent have been prepared and studied as gas chromatographic stationary phases. These coated gas chromatographic columns exhibited good thermal stabilities (230–300 °C) and high efficiencies (1700–2700 plates/m), and were characterized using a linear solvation parameter model in order to understand the effects of the amount of DVB on the features of the resulting composite systems. Their retention behavior and separation efficiencies were demonstrated using the Grob test. By tuning the crosslinking degree for the IL-derived stationary phase, the separation selectivity and resolution of different compounds were improved. The different retention behaviors observed for many analytes indicate that these stationary phases may be applicable as new types of GC stationary phases.