A simple and reliable one-step technique is developed to form robust PAMAM dendrimer–gold nanoparticle nanocomposites using dithiocarbamate-based chemistry. The interparticle spacing and optical properties of films can be readily tuned by controlling the dendrimer generation and/or the mole ratio between dendrimers and nanoparticles. The technique is also used to obtain patterned materials on prepatterned surfaces.