Metal-metal oxide inverse catalysts are valuable in diverse applications, but selecting pairs is challenging. Here, we investigate the role of metal cores (Pt, Ru, Rh, Pd, and Ni) in the formation and dynamics of Brønsted acid sites on the WOxoverlayer on carbon. By in situand ex situcharacterizations, probe chemistry kinetics, and density functional theory (DFT) calculations, we demonstrate that metals with varying work functions promote WOxdispersion and modulate the Brønsted acidity of submonolayer WOxon metal surfaces by tuning the deprotonation energy (DPE) and oxidation state of WOx. The metal core affects the water splitting and hydroxylation of WOx. Water splitting on Ru-WOxis more thermodynamically favorable and has a higher dehydration rate than that on Ni-WOx, leading to an activity enhancement as a result of an increased H2pulsing frequency. This study provides insights into optimizing inverse catalysts.