A bottom-up synthetic methodology to encapsulate pre-synthesized, well-defined gold nanoparticles (AuNPs) into mesoporous titanium dioxide framework (Au@mTiO2 ) is reported. This method employs two structurally and chemically similar templates of amphiphilic block copolymers as well as poly(ethylene oxide)-tethered AuNPs, which showed excellent stability during sol-gel transition and thermal annealing at elevated temperatures. Such synthesis enabled precise control of sizes and loading of AuNPs within the mesoporous TiO2 framework. In light-driven methanol dehydrogenation, the presence of AuNPs significantly enhanced the photocatalytic activity of mTiO2 . This co-template-directed synthesis presents new opportunities to understand the effect of AuNP size in photocatalysis using Au@mTiO2 materials.