Two novel catalysts for anode oxidation of formic acid, Pd₂Co/C and Pd₄Co₂Ir/C, were prepared by an organic colloid method with sodium citrate as a complexing agent. These two catalysts showed better performance towards the anodic oxidation of formic acid than Pd/C catalyst and commercial Pt/C catalyst. Compared with Pd/C catalyst, potentials of the anodic peak of formic acid at the Pd₂Co/C and Pd₄Co₂Ir/C catalyst electrodes shifted towards negative value by 140 and 50mV, respectively, meanwhile showed higher current densities. At potential of 0.05V (vs. SCE), the current density for Pd₄Co₂Ir/C catalyst is as high as up to 13.7mAcm⁻², which is twice of that for Pd/C catalyst, and six times of that for commercial Pt/C catalyst. The alloy catalysts were nanostructured with a diameter of ca. 3–5nm and well dispersed on carbon according to X-ray diffraction (XRD) and transmission electron microscopy (TEM) measurements. The composition of alloy catalysts was analyzed by energy dispersive X-ray analysis (EDX). Pd₄Co₂Ir/C catalyst showed the highest activity and best stability making it the best potential candidate for application in a direct formic acid fuel cell (DFAFC).