Pd/Al2O3catalyst of the “crust” type with Pd loading of 0.03 wt.% was prepared by the deposition of 2 nm Pd particles on the outer surface of the alumina support using laser electrodispersion (LED). This technique differs from a standard laser ablation into a liquid in that the formation of monodisperse nanoparticles occurs in the laser torch plasma in a vacuum. As is found, the LED-prepared catalyst surpasses Pd-containing three-way catalysts, obtained by conventional chemical synthesis, in activity and stability in CO oxidation under prompt thermal aging conditions. Thus, the LED-prepared Pd/Al2O3catalyst showed the best thermal stability up to 1000 °C. The present research is focused on the study of the high-temperature evolution of the Pd/Al2O3catalyst in two reaction mixtures by a set of physicochemical methods (transmission electron microscopy, X-ray photoelectron spectroscopy, and diffuse reflectance UV-vis spectroscopy). In order to follow the dispersion of the Pd nanoparticles during the thermal aging procedure, the testing reaction of ethane hydrogenolysis was also applied. The possible reasons for the high stability of LED-prepared catalysts are suggested.