During the synthesis of gold nanoparticle (NP) assemblies, the interfacial charge and hydrophobicity of the primary particles play a distinguished role. In the present article, we demonstrate that the association of poly(ethyleneimine) (PEI) capped gold NPs with sodium alkyl sulfates provide a powerful route for the manipulation of these interfacial properties. Dynamic light-scattering, electrophoretic mobility, UV-vis-near-infrared spectroscopy, nanoparticle tracking analysis, and transmission electron microscopy measurements were used to characterize the PEI/surfactant/gold nanoassemblies. The results indicate the formation of gold NPs surrounded by a PEI/surfactant shell with composition-dependent charge and hydrophobicity. The mean size and the aggregation of the nanoassemblies can be fine tuned by the amount of surfactant bound to the primary gold NPs as well as by the application of controlled mixing methods. The specific features of the prepared nanocomposites may be further exploited in next-generation applications.