The carbon supported Pd–P (Pd–P/C) anodic catalyst in direct formic acid fuel cell (DFAFC) was prepared with a novel phosphorus reduction method. The Pd–P/C catalyst obtained possesses the high content of P0 in the alloying state. Because alloying P0 could decrease the 3d electron density of Pd and the adsorption affinity of CO and H on Pd, alloying P0 would promote the formic acid (FA) oxidation through the direct pathway. Therefore, the electrocatalytic performance of the Pd–P/C catalyst for the FA oxidation is much better than that of the Pd/C catalyst.