Carbon-supported well-dispersed Pd–Ni–P ternary catalyst targeted for ethanol oxidation reaction (EOR) in alkaline media is synthesized in a simple aqueous bath containing Pd(II) and Ni(II) salts with sodium hypophosphite as the reducing agent and the source for P and sodium citrate as the complexing agent. XRD analysis on the as-prepared Pd–Ni–P/C reveals that Ni shrinks while P expands the Pd lattice structure, and XPS measurement suggests different electronic effects of the two alloying elements on Pd. Cyclic voltammetry and chronoamperometry indicate that the Pd–Ni–P/C presents a remarkably higher electrocatalytic activity than the state-of-the-art Pd/C, Pd–P/C and Pd–Ni/C catalysts. This may be ascribed to the unique electronic, geometric and bifunctional effects involved in this ternary nanoalloy. •Initial synthesis of Pd–Ni–P/C ternary nanocatalyst for ethanol electro-oxidation in alkaline media.•Significantly enhanced electrocatalytic performance on Pd–Ni–P/C compared to that on Pd/C, Pd–P/C or Pd–Ni/C.•Electronic, geometric and bifunctional effects assumed to account for the improved performance.