The strategic integration of metal catalysts with atomic defects in functional materials offers a promising pathway to tailor desired properties. In this study, we demonstrate a high-performance NO2 gas sensor utilizing Pd-sensitized, oxygen vacancy-rich WO3 nanoplates. Pd nanoparticles were precisely deposited on WO3 via atomic layer deposition (ALD), which not only enhanced the oxygen vacancy (Ov) concentration but also optimized the electronic structure of the material. The resulting Pd-WO3-Ov sensor exhibited a significantly improved response of 84.57 to 10 ppm of NO2─3.5 times higher than pristine WO3. The synergistic interplay between Pd catalysts and oxygen vacancies was found to simultaneously lower the operating temperature and amplify both the sensitivity and response speed. Density functional theory (DFT) calculations further confirmed that oxygen vacancies facilitate robust Pd-WO3 interactions, elucidating the mechanism behind the enhanced performance. This work provides a novel design strategy for developing advanced gas sensors through defect and catalyst engineering.