Pt and Pd nanosheaths are successfully synthesized on multi-walled carbon nanotubes (MWCNTs) using the non-covalent poly(diallyldimethylammonium chloride) ( PDDA) functionalization and seed-mediated growth methods. In this method, negatively charged Pt or Pd metal precursors are self-assembled with positively charged PDDA-functionalized MWCNTs, forming uniformly distributed Pt or Pd nanoseeds on MWCNTs supports. The contiguous and highly porous Pt and Pd nanosheath structured catalysts are then formed by the seed-mediated growth in corresponding metal precursors using ascorbic acid as the reducing agent. The essential role of uniformly dispersed Pt and Pd nanoseeds on PDDA-MWCNTs is demonstrated. The results indicate that both Pt and Pd nanosheaths show an enhanced catalytic activity for the methanol and formic acid oxidation reaction in acid solution, respectively, as compared with conventional Pt/C and Pd/C catalysts. The enhanced activities are most likely due to the reduced oxophilicity, which results in a weakened chemisorption energy with oxygen-containing species such as COad, and the increased reactive sites due to the large number of grain boundaries of the Pt and Pd nanosheath structured electrocatalysts. (C) 2009 Elsevier Ltd. All rights reserved.