The grafting of polymers onto synthetic mica surface and formation of an interlayer by the termination of living polymer cation with amino groups introduced onto the synthetic mica was investigated. The introduction of amino groups onto the synthetic mica was achieved by the reaction of silanol groups with gamma-aminopropyltriethoxysilane. It was found that living poly(isobutyl vinyl ether) (polylBVE) and living poly(2-methyl-2-oxazoline) (polyMeOZO) cations with controlled molecular weight and narrow molecular weight distribution were successfully terminated by amino groups of synthetic mica, and the corresponding polymers were grafted onto the surface and interlayer of the mica. The grafting of polyIBVE and polyMeOZO on the synthetic mica decreased with increasing molecular weight of the living polymer cations. The effect of reaction temperature on the grafting of polyMeOZO onto the synthetic mica was examined. The X-ray diffraction curves of polyMeOZO-grafted synthetic mica have a peak at 2theta = 4.5degrees assigned 001 lattice spacing: the lattice spacing was expanded by the grafting of polyMeOZO in the interlayer of the synthetic mica.