Interfaces between catalytically active metal surfaces/sites and metal oxides (such as those formed by metal oxides covering metal nanoparticles by strong metal-support interactions) allow both the metal and metal oxide to react with substrates simultaneously and are important for the activity of many heterogeneously catalyzed reactions. However, similar interactions for well-defined immobilized catalysts have not been investigated, despite their potential for increasing catalytic activity. We test the reactivity of a ruthenium hydride [H2Ru(PPh3)2(Ph2P)2NC3H6Si(OEt)3 (1)] in the amine-promoted hydrogenation of CO2 as both a homogeneous catalyst and anchored on SiO2, Al2O3, ZnO, and SBA-15. Anchoring 1 on the surfaces resulted in varying degrees of surface collapse (formation of H-Ru-O linkages to the surface), with ZnO and confinement in SBA-15 pores giving the least surface collapse. Immobilization of 1 on ZnO gave a 6-fold improvement of the catalytic rate over the corresponding homogeneous catalyst. This increase in the catalytic productivity was only possible when the complex was in close contact with ZnO and is most likely due to a combination of increased catalytic activity and slower deactivation. These results demonstrate the ability of surface effects to vastly improve the productivity of even mediocre catalysts upon surface immobilization.