Pd nanocatalyst is an excellent anode catalyst for alkaline direct methanol fuel cell. The performance of the Pd catalyst can be improved through synergistic effect by adding a transition metal. Carbon nanotube supported non-alloyed Pd-Co bimetallic nano-catalysts were prepared by a step-by-step ethylene glycol reduction method, and their performances for methanol electrooxidation were investigated. The results show that the introduction of Co can improve the dispersion of Pd nanoparticles so as to increase the electrochemical surface area of the catalyst, and significantly improve the kinetic property of the catalyst. The cyclic voltammetry test showed that the peak current density of methanol oxidation over Pd-Co/CNT(1:0.2) catalyst was about 2.7 times that of Pd/CNT catalyst. The chronoamperometry test indicated that Pd-Co/CNT(1:0.2) catalyst had a lower activity decay rate than Pd-Co/CNT catalyst, showing a strong anti-poisoning ability. The improvement in the performance of Pd-Co/CNT catalyst is attributed to the synergistic interaction between Pd and Co. Yet, the current protocol can be used to grow and assemble other multi-metallic catalysts.