Stepped platinum surfaces can become hydrophobic when they are hydrogenated. Even though the Pt(533) and Pt(553) surfaces have similar geometries, the hydrophobicity on the deuterated surface is surprisingly different: on Pt(533) the surface is hydrophobic with water clustering at steps, whereas the entire surface is wet on Pt(553). DOI: 10.1103/PhysRevLett.107.146103 PACS numbers: 68.08.Bc, 68.43.Hn, 82.45.Jn, 82.65.+r Groups of water molecules at an interface have the choice between interacting mostly with the substrate or with each other. This competition lies at the heart of a large variety of phenomena with wetting behavior of surfaces likely being the most well-known example. Contact angle studies date at least as far back as Thomas Young's work from the start of the 19th century [1]. Other important areas where such competition governs physical behavior are, e.g., protein folding and micelle formation [2].For solid surfaces, hydrophilic vs hydrophobic behavior appears difficult to predict. A recent study of water interacting with carbon nanotubes shows that in such confined spaces small changes in temperature may cause a switch between hydrophilic and hydrophobic interaction [3]. Also, minute details of the substrate appear to be of great relevance. A single molecular layer of amorphous solid water is hydrophilic [4], whereas the same layer of crystalline ice is hydrophobic [5].In this Letter, we show that a small change at the atomic level in substrate morphology without changing chemical identity or confinement size may also affect how water molecules adsorb to a surface. A switch from hydrophobic to hydrophilic behavior is not only apparent from drastic changes in H 2 O's desorption characteristics, but also in the chemical reactivity toward H-D exchange at well-ordered platinum surfaces. Our results impact on general thinking on long-range ordering of water molecules at interfaces and pose opportunities in tailoring chemistry occurring on nanoparticles as used in, e.g., heterogeneous catalysis and electrochemistry.As a substrate, we use single crystalline platinum discs, cut and polished to expose either the (533) or (553) surface. Schematic representations of these surfaces for top and side views are shown in Fig. 1 with every circle representing a Pt atom. The only difference between these surfaces is the step type that separates the 4-atom wide (111) terraces. The (533) surface contains the steeper (100) step type, whereas the (553) surface has the more gently sloped (110) step type. The angles that the singleatom high steps make with the terraces are, respectively, 116.6 and 125.3 . Our platinum surfaces are cleaned and studied under ultrahigh vacuum (UHV) conditions. Details on experimental procedures can be found in the Supplemental Material [6]. Low energy electron diffraction (LEED) confirms the atomic ordering of the surface as depicted in Fig. 1.The cleaned platinum surfaces are first exposed to D 2 by background dosing until no more dissociation occurs. To minimize contamination by H, t...