Reconstruction of a clean surface of a platinum catalyst and a platinum surface covered with gold during ammonia oxidation was studied by SEM observations. It was found that the process of catalytic etching had two sequential stages in which different crystal structures with different rates of growth formed on the surface. The first stage was the formation of parallel facets, and the second stage was the formation of individual microcrystals with perfect crystal faces. It was also found that the second stage had a threshold character, beginning after some delay from the start of the reaction. A structure resembling metal wool and consisting of interlaced platinum filaments was found to form on the surface of gold-covered platinum catalysts. Characteristic features of this structure’s development are reported. The growth of filaments is attributed to the vapor-liquid-solid mechanism of whisker growth. On the basis of the observed platinum whisker formation and behavior during ammonia oxidation, a mechanism of catalyst surface reconstruction that explains observed characteristic features of the process of catalytic etching is proposed.