Palladium (Pd), has demonstrated promising electro-catalytic activity for formic acid oxidation, but suffers from extremely low abundance. Recently alloying with a transition metal has been considered as an effective approach to reducing the loading of Pd and enhancing the activity of Pd-based catalysts simultaneously. Herein, carbon supported PdFe nanoparticles (NPs) are synthesized at room temperature by using sodium borohydride as reducing agent and potassium ferrocyanide as Fe precursor. The Pd50Fe50 alloy sample annealed at 900 degrees C for 1 h shows the best catalytic activity among PdxFe1-x (x = 0.2, 0.4, 0.5, 0.6, and 0.8) towards formic acid oxidation. To further improve both catalytic activity and stability, the ultra-low Pt (0.09 wt %) decorated Pd50Fe50 NPs (PtPd/PdFe) are prepared via the galvanic replacement reaction. Compared with Pd50Fe50/C, the PtPd/PdFe/C Exhibits 1.52 times higher catalytic activity and lower onset potential (similar to 0.12 V). The significant enhancements of formic acid oxidation can be attributed to the accelerated dehydrogenation reaction of formic acid by Pt atomic clusters. Moreover, the PtPd/PdFe/C also demonstrates better tolerance to poisons during formic acid oxidation. (C) 2016 Elsevier Ltd. All rights reserved.