By taking advantage of the non-equilibrium synthetic conditions, the cathodic corrosion method was used to prepare a selected a number of alloys of which solid-solution alloys do not exist under ambient conditions. To illustrate our finding we present the preparation at room temperature of PtBi and PtPb alloy nanoparticles with various compositions. These alloys have shown benchmark mass activity and durability towards the formic acid oxidation. The improvement in the catalytic activity is explained based on the composition of the metal alloys, the reduced particle size and, quite importantly, the level of cleanliness of the catalyst obtained by this method.