We used an aqueous leaf extract of Camellia sinensis to synthesize Ag nanoparticles (AgNPs). A layer of ca. 6 nm around a group of the AgNPs in which the inner layer is bound to the AgNPs surface via the hydroxyl groups of catechin has been observed. TEM analysis of AgNPs showed the formation of truncated triangular nanoplates and/or nanodisks and spherical with some irregular-shaped polydispersed nanoparticles in absence and presence of shape-directing cetyltrimethylammonium bromide. The polyphenolic groups of epigallocatechin-3-gallate (EGCG) are responsible for the rapid reduction of Ag(+) ions into metallic Ag(0). The free -OH groups are able to stabilize AgNPs by the interaction between the surface Ag atoms of AgNPs and oxygen atoms of EGCG molecules.