The carbon supported Pd(Pd/C) catalyst modified by the new polyoxometalate with Keggin type of Sn-Substituted structure (K7CoW11O39SnOH)-W-11-O-IV (Pd/C-K-7) catalyst is prepared with the simple impregnation reduction method. This work investigates the effects of Pd/C K7 catalyst for direct formic acid fuel cells (DFAFCs). The morphology, structure, size and composition of the Pd/C K7 catalyst are characterized by transmission electron microscopy (TEM) energy dispersive spectrum (EDS), X-ray diffraction (XRD). Cyclic voltammetry, chronoamperometry and CO-stripping voltammetry tests demonstrate the Pd/C K7 catalyst have higher electrocatalytic activity, better electrochemical stability, and higher resistance to CO poisoning over the unmodified Pd/C catalyst for the formic acid oxidation reaction (FAOR) owing to (K7COW11O39SnOH)-W-11-O-IV with Keggin structure. Therefore, the Pd/C-K7 catalyst could be used as the excellent anodic catalyst in DFAFCs. (C) 2014 Elsevier B.V. All rights reserved.