The location and coordination of Cu(II) cation-doped mesoporous material produced by the calcination of organophilic silicate-bearing hectorite were characterized by electron spin resonance and electron spin echo modulation spectroscopic methods. One Cu(II) species (g(II) = 2.34, g perpendicular to = 2.05, and A(II) = (142-148) x 10(-4) cm(-1)) was obtained after air-drying and vacuum-drying. After the adsorption of water and methanol, one cm type of Cu(II) complex (g(II) = 2.34, g perpendicular to = 2.05, and A(II) = (142-149) x 10(-4) cm(-1)) is observed. These studies indicate the presence of a distorted octahedral cupric species in the mesopore region. Under air-drying and vacuum-drying, electron spin echo modulation indicates that Cu(II) cations are coordinated to silicate pillars in the interlayer region. In the hydrated sample, the Cu(II) ions directly bind to three water molecules and interact with one, more distant, water molecule. In a methanol-adsorbed sample, the Cu(II) ions directly coordinate to one methanol and indirectly coordinate to another methanol molecule.