Different gold microstructures have been synthesized by using supramolecular gold(i) organometallic compounds as templates and Ag nanoparticles as reducing agents. The use of fibers resulting from supramolecular assemblies of neutral gold(i) compounds gives rise to the formation of microrods. The use of supramolecular assemblies from ionic molecules results in spherical or square-based prism gold microstructures, depending on the shape of the supramolecular gold(i) precursor assembly. In addition to temperature and reaction time, solvents exert a strong influence on the formation and morphology of gold structures, as borne out by the example that well-defined star-like morphologies have been obtained in chloroform.