Highly tectonized contact between serpentinite and younger pegmatite in the magnesite mine of Wiry contains various layer silicates. Vermiculite, chlorite, smectite, and interstratified mica-vermiculite were recognized by means of routine XRD examination. Two three component interstratifications of mica-vermiculite-chlorite and chlorite-swelling chlorite-smectite were identified by a combined procedure of deconvolution of the XRD patterns and simulation of XRD tracings. A mineral with large diffraction maxima, displaying “chlorite intergrade” characteristics, appeared to be a mixture of chlorite, mixed layer chlorite-smectite, and vermiculite. Polytypes of phyllosilicates were determined by the X-ray transmission method. Due to the heritage of parent mineral polytype structure by transitional products of alteration, two distinct sequences of layer silicates were observed: one formed from trioctahedral mica (vermiculite, mixed layer mica-vermiculite); and one evolved from chlorite (e.g., mixed layer chlorite-swelling chloritesmectite). A tentative scheme of the primary contact zone structure, not obscured by subsequent brittle tectonics either by transformation of layer silicates, is proposed.