Palladium in the concentration of 0.04–0.5 mass % was deposited on carbon nanofibres with the stack structure. The state of finely dispersed palladium nanoparticles deposited on the carbon nanofibres was studied by physical methods. Decrease of the concentration of supported palladium on the carbon nanofibres below 0.2 mass % led to the stabilization of the metal in atomic state. It was found that palladium nanoparticles in the atomic state were responsible for the high selectivity of the catalyst in acetylene hydrogenation to ethylene. Doping of carbon nanofibres by nitrogen atoms substantially alters the properties of supported palladium nanoparticles. The activity of the catalysts decreases whereas their selectivity substantially increases