The catalytic activity of the Pt(110) surface for the reaction of NO + H-2 was much less than that of the Pt(100) surface. However, the catalytic activity of the Rh deposited Pt(110) surface was almost equal to that of the Rh deposited Pt(100) surface. That is, the catalytic reaction of NO + H-2 on Pt(110) and Pt(100) surfaces is highly structure sensitive, but it changes to structure insensitive by the deposition of Rh atoms. These results are rationalized by formation of an active overlayer on the Pt(110) and Pt(100) surfaces, which is very analogous to the Rh-O/Pt-layer formed on Rh/Pt(100), Pt/Rh(100) and Pt-Rh(100) alloy surfaces during catalysis. The formation of the common overlayer of Rh-O/Pt-layer during catalysis is responsible for the structure insensitive catalysis of Rh deposited Pt-based catalysts, which is an important role of Rh in a three way catalyst.