A series of Pd–Co bimetallic nanostructures with Co compositions ranging from 0 to 13 at.% were fabricated on glassy carbon electrode by one step electrodeposition in the presence of polyvinylpyrrolidone (PVP). The roles of PVP and Co have been systematically investigated by using combined techniques such as scanning electron microscopy, energy dispersive spectrometry, cyclic voltammetry, X‐ray diffraction, and chronoamperograms. PVP was used as an additive to stabilize the Pd nanoparticles and inhibit agglomeration during their formation. The prepared Pd100Co10 bimetallic nanostructures exhibited great catalytic activity towards ethanol oxidation in alkaline, which implies that low Co doping can be a convenient way to enhance the electrocatalytic property of Pd. The present study shows that the Pd/Co bimetallic nanoparticulate can be a promising catalyst for portable applications in direct ethanol fuel cell in alkaline solution.