Activated carbon was modified with phosphotungstic acid (PWA) by impregnation. Palladium-cobalt (PdCo) alloy nanoparticles were loaded on the hybrid supports (PWA-C) to prepare PdCo/PWA-C catalyst by liquid reduction method. Uniformly dispersed catalyst nanoparticles were prepared and their average particle sizes are in the range of 3.0-5.0 nm. Electrochemical measurements demonstrated that the activity of the PdCo/PWA-C catalyst was enhanced than home made Pd/C catalyst as a factor of 2.16 for formic acid oxidation. A negative shift (66 mV lower than Pd/C) of the CO stripping current peak and improved stability (5.28 times higher than Pd/C) were observed for the PdCo/PWA-C catalyst. The amount of decomposed formic acid over the PdCo/PWA-C catalyst is only 36% of the Pd/C catalyst, which indicated the excellent inhibition performance of the decomposition of formic acid for the PdCo/PWA-C catalyst. In addition, faster charge-transfer kinetics of the formic acid oxidation for the PdCo/PWA-C catalyst was found through Tafel slope measurements. The better electrocatalytic activity and stability of PdCo/PWA-C catalyst may be attributed to the synergistic effect of the PWA modification and Co alloying.The direct formic acid fuel cell (DFAFC) can be used as the power source for mobile electronic devices due to its several advantages, such as high energy conversion efficiency, low environmental pollution, and low operating temperature. Previous studies have proved that formic acid can be oxidized at less positive potential and with faster kinetics than methanol, and the crossover of formic acid through the polymer membrane is also lower than that of methanol. 1,2 According to the previous research, the direct pathway for oxidation to CO 2 is the preferred pathway on Pd, which avoids catalyst poisoning. 3 On the contrary, adsorbed CO at Pt-based catalyst leads to the deactivation of catalyst. Therefore, Pd is more effective than Pt for formic acid electrocatalytic oxidation. 4-8 In order to improve the activity, stability, and decrease the loading of Pd for the Pd-based catalyst, another metal were used to be alloying with Pd, such as Pd-Co, 9 Pd-Au, 10