The fabrication and catalytic properties of hierarchical porous carbon loaded with PtRu particles was studied. A silica nanoparticles opal is filled with resorcinol/formaldehyde resin, which is then pyrolized to form a macroporous carbon. Depending on synthesis conditions the volume contraction induces mesopore formation in the macroporous carbon, creating a hierarchical porous carbon (HPC). The material consists of a thick, highly porous electrocatalytic film. PtRu nanoparticles were loaded inside the HPC by reduction of metallic ions with formic acid. The electrocatalytic activity toward CO and methanol oxidation was evaluated. The current densities for methanol electrooxidation at 60 °C (220 μA cm−2 and 120 Ag−1 at 0.55 VRHE) reveals high activity, suggesting that the catalysts consist of well disperse, small PtRu nanoparticles, with a low degree of agglomeration and good accessibility for reactants.