Spin coating a dilute solution of thiol-passivated Au nanoparticles onto silicon produces nanostructured cellular networks. Photoemission measurements, coupled with atomic force microscopy imaging and a statistical crystallography analysis, show that although annealing in the 500–600 K range removes the thiol surfactants surrounding the nanoparticles, the cellular morphology of the nanocrystal foam is preserved following annealing. Thus, self-assembled nanocrystal arrays may be exploited as templates for (bare) Au nanostructures on Si. Although appreciable particle diffusion during annealing does not occur, significant sintering of Au nanocrystals within the cellular network branches is observed.