In this study, we report a synthesis of small size, well-dispersed, and durable metal alloy nanoparticles based on palladium for direct liquid fuel cells: It achieved by supramolecular self-assembly of surfactant on the carbon supporter and polymer protective coating with ion impregnation. From the physical analysis, we confirm that the particle size and dispersion uniformity of synthesized Pd-based alloy nanoparticles was comparable to those synthesized by micro-emulsion methods. The resulting palladium based alloy nanoparticles exhibits superior electrocatalytic activities, especially long-term stability, toward electro-oxidation of formic acid and alcohols than those of palladium nanocatalysts. This work not only offers a powerful route to the synthesis of Pd-based alloy catalyst but also provides important possibility to solving the bottleneck of direct liquid fuel cell anode catalyst.