Aqueous micellar solutions of F68 (PEO78-PPO30-PEO78) and P103 (PEO17-PPO60-PEO17) triblock polymers were used to synthesize gold (Au) nanoparticles (NPs) at different temperatures. All reactions were monitored with respect to reaction time and temperature by using UV-visible studies to understand the growth kinetics of NPs and the influence of different micellar states on the synthesis of NPs. The shape, size, and locations of NPs in the micellar assemblies were determined with the help of TEM, SEM, and EDS analyses. The results explained that all reactions were carried out with the PEO-PPO-PEO micellar surface cavities present at the micelle-solution interface and were precisely controlled by the micellar assemblies. Marked differences were detected when predominantly hydrophilic F68 and hydrophobic P103 micelles were employed to conduct the reactions. The UV-visible results demonstrated that the reduction of gold ions into nucleating centers was channeled through the ligand-metal charge -transfer complex (LMCT) and carried out by the surface cavities. Excessive hydration of the surface cavities in the case of F68 micelles produced a few small NPs, but their yield and size increased as the micelles were dehydrated under the effect of increasing temperature. The results concluded that the presence of well-defined predominantly hydrophobic micelles with a compact micelle-solution interfacial arrangement of surface cavities ultimately controlled the reaction.