A catalyst of the Pt-Ru/C doped with Eu for methanol electro-oxidation were synthesized by the method of pulse electro-deposition of the precursor of active material impregnated in porous carbon black layer. The active stability of Pt-Ru-Eu/C was evaluated using cyclic voltammetry. And the microstructure and composition of the catalyst surface were characterized by XRD and XPS. Results show that the performances of Pt-Ru-Eu/C for methanol electro-oxidation went down slowly during the cycles of number 15 to number 50, and then went into the steady state after the cycle of number 65. However, the electro-catalytic activity of Pt-Ru-Eu/C is still higher than that of Pt-Ru/C in all the cycles of the activity test. The main reason of the low activity for methanol electro-catalytic oxidation on the Pt-Ru-Eu/C is the serious loss of the EuOx from the top atom layer and the increasing of the size of Pt-Ru-Eu alloy particles with the activity test time prolonging