The supramolecular structural aspects of hetero-assemblies constituted of gold nanoparticles capped with amphiphilic unimolecular micelles were studied using synchrotron-based small angle X-ray scattering (SAXS). Experimental results revealed that straightforward transfer of citrate-capped Au nanoparticles from an aqueous environment to a toluenic solution of amphiphilic hyperbranched polymers results in the spontaneous integration of the nanocrystals into the extended hydrophilic domains of self-assembled supramolecular structures. In this way, we were able to self-organize metal-polymer nanoarchitectures in solution displaying interesting thermoactive functions, i.e.: hybrid assemblies exhibiting negative thermal expansion coefficients. We consider that this strategy has potentiality to realize self-organized supramolecular hetero-assemblies as it provides an alternative methodology to spontaneously integrate nanoscale building blocks into preformed supramolecular objects. (c) 2013 Elsevier Inc. All rights reserved.