The current work utilizes the adsorption of hydrogen and the hydrogenation of cyclohexene as probe reactions to bridge the materials gap between single crystal and polycrystalline Ni/Pt bimetallic surfaces. Previous studies on Ni-modified Pt(1 1 1) have identified the formation of a Pt-Ni-Pt(1 1 1) subsurface structure that binds atomic hydrogen and cyclohexene more weakly, leading to a low-temperature hydrogenation pathway not present on either of the parent metal surfaces. In the current work, the Pt-Ni-Pt subsurface structure is prepared by depositing Ni on a polycrystalline Pt foil substrate. The adsorption of hydrogen and hydrogenation of cyclohexene are investigated using surface science experiments and density functional theory (DFT) calculations. The polycrystalline Pt-Ni-Pt subsurface structure shows general similarities to Pt-Ni-Pt(1 1 1) in the low-temperature hydrogenation pathway, demonstrating the validity of using single crystals to predict activity trends for more complex surfaces. (C) 2011 Elsevier Inc. All rights reserved.