We present here an extensive study on the electrocatalytic activity of varying compositions of Pd_100−xCu_x (100 ≤ x ≤ 0) catalysts towards the electrooxidation of ethanol and ethylene glycol (EG). The Pd_100−xCu_x catalysts were electrochemically synthesized and characterized by field-emission scanning electron microscopy, energy-dispersive X-ray analysis, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. Electrochemical investigations were carried out by means of cyclic voltammetry, linear sweep voltammetry and chronoamperometry studies in 1 M KOH and the respective alcohols. The electrocatalytic activity of the Pd_100−xCu_x catalysts was quantified by their mass activity (mA mg⁻¹) and onset potential (V vs. RHE). It turned out that the catalysts Pd₉₀Cu₁₀, Pd₈₀Cu₂₀ and Pd₇₀Cu₃₀ exhibited enhanced activity compared to pristine Pd for both the alcohols. On the other hand, the Pd₆₀Cu₄₀ and Pd samples exhibited a similar performance towards ethanol oxidation implying possible attractive substitution of 40% Pd with Cu, which will remarkably reduce the cost of the Pd electrocatalyst for direct alcohol alkaline fuel cell applications. For EG oxidation, the Pd₈₀Cu₂₀ and Pd₇₀Cu₃₀ catalysts exhibited stable performance accompanied by high mass activity. The combined effects of electronic coupling between Pd and Cu and the preferential oxophilicity of copper in the PdCu alloy are ascribed to be responsible for such an enhanced electrocatalytic activity.