Pyrene-substituted amphiphilic ATRP polymers (P1) were used to stabilize the pyrene-substituted gold(i) NHC complex (Au-1) within the hydrophobic compartment of micellar structures in a methanol/water mixture through non-covalent π-π stacking interactions. The stacking interactions between pyrene groups of the polymer and the catalyst were investigated by means of fluorescence spectroscopy by comparing excimer and monomer emission signals of the pyrene moiety. The supported catalyst (Au-1@P1) formed spherical micellar structures in a water/methanol mixture with an average size of 55.6 (±13.1) nm as confirmed from TEM analysis. The performance of the catalytic system was tested on alkyne hydration reactions of alkynes. When compared to the unsupported analog, the supported catalyst showed an improved performance as a result of stabilization through π-stacking interactions within the hydrophobic compartment in the micellar structure.