Copper particles were deposited on the surface of palladium decorated buckypapers by the means of chemical plating, in which the palladium nanoparticles act as catalyst for initiating the reduction of complexed Cu2+ ions in the presence of formaldehyde. By adjusting the plating time, it is possible to tune the size of the highly crystalline copper particles and at the same time control the coverage of the metal on the surface of carbon nanotubes. In a subsequent step, the copper particles were partially exchanged with palladium to obtain bimetallic CuPd nanoparticles on the nanotubes by applying galvanic replacement reactions in aqueous solution of Pd2+ ions. Sufficiently high electrical conductivity of both Cu and CuPd/buckypaper composites makes them suitable to be used as electrocatalytic electrodes. The electrochemical properties of the different electrode materials were also evaluated by the model reaction of methanol electrooxidation. The degradation mechanism of copper and CuPd bimetallic catalysts were systematically studied by employing surface characterization techniques on the composite films after electrocatalytic testing in alkaline solution in the presence and absence of methanol. Chronoamperometric test of the catalysts/buckypaper composites had revealed that palladium plays a protecting role in CuPd bimetallic structure during methanol electrooxidation.