Organofunctionalized phyllosilicates containing both amino and mercapto groups were synthesized and used as support for silver nanoparticles in situ deposition. Depending on silver concentration in relation to phyllosilicate different amount of nanoparticles size and distributions were obtained, even with smallest silver used causes strong exfoliation of the phylosilicate lamella. Also such condition favors nanoparticles formation with homogeneous distribution with smaller diameters and narrower particle particles size distributions. With highest silver amounts preferential external phyllosilicate surface crystallization is obtained, as given by particle diameters up to 30 nm. Scanning and transmission electron microscopies were successfully employed to characterize morphological and structural features for these synthesized materials, enabling atomic visualization for the silver nanoparticles. These new phyllosilicates containing silver nanoparticles are extensively employed to design inorganic light emission diodes and also in applying in biological fields.