The unique properties of gold at the nanoscale have favored application in a variety of fields from catalysis to targeted drug delivery; moreover, the reactive nature of gold nanoparticles allows its use as an active center for nanoreactors. This study presents the controlled synthesis of unsupported nano reactors with self-assembled polymers as template and gold incorporated as active centers. Gold (I) chloride was found to react with the hydrophilic domain of the template and produce metal gold sheets of 30-50 nm in size, as well as with the hydrophobic cavity to produce metal gold clusters, 2-3 nm in size. The size of gold nanostructures was characterized by High Resolution TEM, while the interaction between gold and polymer was confirmed by molecular modelling. The careful spectroscopic characterization including UV Vis and IR allowed to differentiate clusters and sheets and to follow the growth of the gold particles. The control of the environment surrounding the active center (hydrophilic versus hydrophobic domains) is essential for the development of tailored nanoreactors. The control of the interaction between the polymer and gold was obtained by modifying the nature of the polymer and external energy. It was found that the presence of monomethyl ester in the polymer intensifies the interaction of gold on the hydrophilic domain while producing larger gold sheets (both hpc and fcc) and slightly smaller gold clusters. Sonication was found to disrupt the whole self-assembly process and completely eliminate the interaction of gold with the hydrophobic cavity producing exclusively atomically thin layers of hpc gold. The ability to control the interaction of gold with the hydrophobic or hydrophilic cavity offers tremendous potential for many applications from drug delivery to nanocatalysis in hydrophilic and hydrophobic confinement. Crown Copyright (C) 2017 Published by Elsevier B.V. All rights reserved.