Pd-Based anode catalysts suffer from low stability, weak resistance to poisoning and high costs due to the use of precious metals, which affects the application and commercialization of DAFCs. Therefore, the preparation of high-activity, high-stability, anti-poisoning ability and low-cost catalysts has become extremely important for large scale application. In this book, we developed and designed excellent and ultra-stable Pd-based nanocatalysts for DAFCs by studying the structural effect, support composition and elements advantages, through applying different synthesis strategies and using the cheapest precursors. Specifically, the combination of Sn, Ag and Cd with Pd NPs was investigated to provide an optimized structure that enhanced the electrochemical performance of MOR and EOR. (i) Carbon supported Pd-Sn nanoparticles were prepared by simple method on functionalized carbon supports towards EOR in alkaline medium. (ii) The PdAg/MWCNTs anode NPs nanocatalysts were successfully prepared via facile one-step room temperature synthesis strategy without addition of any capping agents towards MOR and EOR.