Multiwall carbon nanotubes supported Pd–Co electrocatalysts (Pd–Co/MWCNTs) for hydrazine electrooxidation in alkaline electrolytes were prepared. Their morphology and structure were characterized by scanning electron microscopy, transmission electron microscope, and X‐ray diffraction. The effect of the mass ratio of Pd to Co on the catalytic performance was examined via cyclic voltammetric and chronoamperometric measurements. The Pd–Co/MWCNTs with a mass ratio of 1:1 for Pd:Co shows higher catalytic performance than both Pd/MWCNTs and Co/MWCNTs and it has good stability for catalyzing the electrooxidation of hydrazine. The gas collection measurements indicated that hydrazine electrooxidation on Pd–Co/MWCNTs proceeded via a near 4‐electron pathway.