In the current study, well-defined PdCo porous nanostructure (PdCo PNS) is prepared by a simple one-pot wet-chemical method and polypyrrole@multi-walled carbon nanotubes (PPy@MWCNTs) nanocomposite is used as a catalyst support. The morphology and the structural properties of the prepared catalyst were studied by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The electrocatalytic performance of PdCo PNS/PPy@MWCNTs on glassy carbon electrode has been evaluated by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) techniques. The specific activity of PdCo PNS/PPy@MWCNTs for ethanol electrooxidation (1.65 mA cm −2 ) is higher than those of other compared electrocatalysts. Also, PdCo PNS/PPy@MWCNTs catalyst repre- sented higher electrocatalytic activity, better long-term stability and high level of poisoning tolerance to the carbonaceous oxidative intermediates for ethanol electrooxidation reaction in alkaline media. Fur- thermore, the presence of PPY@MWCNTs on the surface of GCE produce a high activity to electrocatalyst, which might be due to the easier charge transfer at polymer/carbon nanotubes interfaces, higher elec- trochemically accessible surface areas and electronic conductivity. The superior catalytic activity of PdCo PNS/PPy@MWCNTs suggests it to be as a promising electrocatalyst for future direct ethanol fuel cells.