Networked nanowire (NNW)-structured catalysts have attracted extensive attention due to their large surface area and structural stability, which mean that they have excellent catalytic activity and stability and can be used as anode reaction catalysts for use in direct alcohol fuel cells (DAFCs). Herein, a series of networked PdSn nanowires synthesized via a modified polyol strategy are used as efficient DAFCs anode reaction catalysts. The introduction of Sn plays an important role in the improvement of catalytic behavior, in which the existence of Sn promotes the oxidation of intermediates by providing abundant oxyphilic species. Moreover, the generated PdSn NNWs-3 with optimal content show rich grain boundaries and an even NNW structure, which provides more active sites to further improve catalytic performance, so it exhibits excellent activity toward alcohol oxidation. The mass activities of PdSn NNWs-3 toward the ethanol oxidation reaction (EOR) and the methanol oxidation reaction (MOR) are 8105.0 and 3099.5 mA mgPd-1, which are 6.9 and 10.7 times higher than those of Pd/C, respectively. Compared with Pd/C, the PdSn NNWs also display enhanced stability towards the EOR and MOR. This work demonstrates that NNW nanocatalysts indeed exhibit excellent catalytic performance for alcohol oxidation reactions.