Multiwalled carbon nanotubes (MWCNTs) supported palladium-phosphorus nanoparticles (Pd–P/MWCNTs) catalyst is synthesized by homogeneous precipitation–reduction reaction method using hypohosphite as reducing agent. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis confirm that some P has entered into the crystal lattice of Pd and thus the Pd–P alloy is formed. Transmission electron microscopy (TEM) images reveal that Pd–P nanoparticles are uniformly dispersed on MWCNTs and the average particle size of Pd–P/MWCNTs catalyst is very similar to that of Pd/MWCNTs catalyst prepared by using NaBH4 as reducing agent. Cyclic voltammetric and chronoamperometric experiments show that the electrocatalytic activity and long-term operation stability of Pd–P/MWCNTs catalyst are better than that of Pd/MWCNTs catalyst for ethanol electrooxidation in alkaline media, indicating that the addition of P in Pd nanoparticles can promote the electrocatalytic activity and stability of Pd catalyst for ethanol electrooxidation.