Cupric ion-doped, alumina-pillared tetrasilicic mica (Cu-Al-13-TSM) was synthesized and characterized by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopic methods. Under air-dried and vacuum-dried conditions, one Cu(II) species was observed. One type of Cu(II) complex is observed with the adsorption of water, methanol, and ethylene. These studies indicate the presence of a distorted octahedral cupric species in the micropore region that is directly bound to three water molecules and presumably to three oxygen atoms of the interlayer surface. In the methanol-adsorbed sample, the Cu(II) ions directly coordinate to one methanol and indirectly coordinate to another methanol. In the ethylene-adsorbed sample, the Cu(II) ions directly coordinate to one ethylene molecule.