Abstract The challenge of hydrogen atom (H*) poisoning active sites during dehydrogenation has severely limited the application of liquid organic hydrogen carriers (LOHCs). While hydrogen spillover has been extensively studied in hydrogenation reactions, its potential to enhance dehydrogenation kinetics remains unexplored. This work demonstrates a progress by repurposing this fundamental phenomenon to address the critical bottleneck in LOHC dehydrogenation. A tungsten‐doped alumina (WAlO) support was engineered to create atomic‐scale spillover pathways. The Pt/WAlO catalyst achieved a remarkable dehydrogenation degree of 86.61%. Through the in situ DRIFTS and H 2 ‐TPR, tungsten doping is demonstrated to generate oxygen vacancies which act as hydrogen sinks, promoting H* migration. DFT calculations confirm a reduced energy barrier for H* migration. The generalizability of this strategy is further demonstrated across multiple LOHC substrates. This study successfully expands the application scope of hydrogen spillover beyond conventional hydrogenation processes, paving the way for designing efficient LOHC dehydrogenation catalysts.