An alkylimidazolium-based long-chain ionic liquid (LCIL) was immobilized in silica nanopores via a supramolecular assembly approach. To discuss the characteristic features of LCIL in a confined nanospace, except for the characteristics of the host materials, we have prepared the silica host with monodisperse morphology and a nanostructured system to immobilize LCIL. The nanostructure is composed of three distinct regions: the silica framework, the hydrophobic interior of the alkyl chains, and the organic-inorganic ionic interface. Anomalous CO(2) adsorption sites were found to be well-ordered locations on the ionic interface fabricated by the π-π-stacked imidazolium heads containing inorganic anions and polar silica surfaces.