In this study, a highly efficient carbon‐supported Pd catalyst for the direct ethanol fuel cell was developed by electrodepositing nanostructured Pd on oxygen plasma‐treated carbon fiber paper (Pd/pCFP). The oxygen plasma treatment has been shown to effectively remove the surface organic contaminants and add oxygen species onto the CFP to facilitate the deposition of nano-structured Pd on the surface of carbon fibers. Under the optimized and controllable electrodeposi-tion method, nanostructured Pd of ~10 nm can be easily and evenly deposited onto the CFP. The prepared Pd/pCFP electrode exhibited an extraordinarily high electrocatalytic activity towards eth-anol oxidation, with a current density of 222.8 mA mg−1 Pd. Interestingly, the electrode also exhibited a high tolerance to poisoning species and long‐term stability, with a high ratio of the forward anodic peak current density to the backward anodic peak current density. These results suggest that the Pd/pCFP catalyst may be a promising anodic material for the development of highly efficient direct alcohol fuel cells.