The synthesis of multifunctional poly(amidoamine)(PAMAM)-based dendrimers containing a cleavable disulfide linkerwithin each armof the dendrimer, together with condensable triethoxysilyl groups on the periphery of the dendrimer, isdescribed. The dendrimers were mixed with bis(triethoxysilyl)benzene and subsequently transformed into silsesquioxanegels or periodic mesoporous organosilicas (PMOs) to generate materials with dendrimers covalently embedded within theinterior of the silsesquioxane networks. Subsequent treatment of the gels with dithiothreitol enabled the core of thedendrimers to be selectively cleaved at the disulfidesite, thus generating thiol functions localised within the pores.The effect of different dendrimer generations on the reactivity of the pendant thiol functions was probed by impregnationwith gold salts, which were reduced to obtain gold nanoparticleswithin the pore networks of the gels and PMOs. The gelsyielded polydisperse gold nanoparticles (2 to 70 nm) with dimensions modulated by the generation of the dendrimer,together with well-defined gold/thiolate clusters with Au...S distances of 2.3 Å. Suchclusters were also observed in the PMOsystem, together with monodispersed gold nanoparticles with diameters comparable to that of the organised pores in thePMO. The role of surface functionalisation in controlling the formation of gold clusters and/or nanoparticles is discusse