Pd and PdAu catalysts supported on SBA15 and SiO2 were prepared and investigated for H2O2 direct synthesis in a batch autoclave (10 °C and 17.5 bar) and in the absence of halides and acids. The SiO2 supported catalysts exhibited inferior performances compared to the mesoporous ordered SBA15. A good control of both the catalysts dispersion and nanoparticle stability was achieved using SBA15. Catalysts were doped with bromine, a promoter in the H2O2 direct synthesis. Productivity and selectivity decreased when bromine was incorporated in the catalysts, thus indicating a possible poisoning due to the grafting process. A synergetic effect between Pd and Au was observed both in presence and absence of bromopropylsilane grafting on the catalyst surface. Three modifiers of the SBA15 support (Al, CeO2 and Ti) were chosen to elucidate the influence of the surface properties on metal dispersion and catalytic performance. Higher productivity and selectivity were achieved incorporating Al into the SBA15 framework, whereas neither Ti nor CeO2 improved H2O2 yields. The enhanced performance observed for the Prau/Al–SBA15 catalysts was attributed to the increased number of Bronsted acid sites. A modification of this catalyst with bromine was confirmed to impair both productivity and selectivity, possibly due to the broader particle size distribution and the poor stability of the metal nanoparticles, as demonstrate by transmission electron microscopy (TEM) images. H2O2 disproportionation was also investigated. A much slower reaction rate was observed compared to the H2O2 production, suggesting that the major contributor in the process of H2O2 destruction must be connected to the hydrogenation reaction.