Pt-based direct methanol fuel cells are attracting increasing interest as environmentally-friendly alternative energy sources. However, the high price of Pt and the difficulty to prepare favourable morphologies for catalysis (e.g., mesoporous materials) is hampering its development into feasible products. Here, we demonstrate a novel approach to efficiently grow mesoporous films of Pt-poor alloys (Co3Pt and CoPt3), based on electrodeposition in ionic liquid-in-water (IL/W) microemulsions. The high proportion of the electrolytic aqueous solution in the IL/W microemulsion favors a significant deposition rate, while the presence of IL drops induces the formation of highly mesoporous films. The mesoporous alloys, with pores in the 30-40 nm range, exhibit excellent durability in acidic and alkaline aggressive media, maintaining their peculiar morphology. The structures are very efficient for the catalysis of methanol electro-oxidation in alkaline medium, with minimal poisoning of the catalysts. These results pave the way to develop simple, versatile environmentally friendly fuel cells catalysts, to commercialize new viable ecological alternative energy sources.