We have examined the role of the internal environment of dendrimer templated silicanetworks in tailoring the construction of silver nanoparticle assemblies. Silica networksfrom which 3,5-dihydroxybenzyl alcohol based dendrimer templates have been completelyremoved, slowly wet with an aqueous solution of silver acetate. The latter then reacts withinternal silica silanol groups, leading to chemisorption of silver ions, followed by the growthof silver oxide nanoparticles. Silica network constructed using generation 4 dendrimercontains residual dendrimer template, and mixes with aqueous silver acetate solution easily.Upon chemisorption, silver ions get photolytically reduced to silver metal undera stabilizing dendrimer environment, leading to the formation of silver metalnanoparticles.