This study investigates the impact of atomic defects, such as oxygen vacancies and Ce3+ ions, on cerium oxide (ceria) surfaces during chemical mechanical polishing (CMP) for silica glass finishing. Using density functional theory (DFT) and reactive molecular dynamics simulations, the interaction of orthosilicic molecules and silica glass with dry and wet ceria surfaces is explored. Defects alter the surface reactivity, leading to the dissociation of orthosilicic acid on oxygen vacancies, forming a strong Si-O-Ce bond. Hydroxylated surfaces exhibit easier oxygen vacancy formation and thermodynamically favored substitution of hydroxyl groups with orthosilicic acid. A new ReaxFF library for silica/ceria interfaces with defects is validated using DFT outcomes. Reactive MD simulations demonstrate that ceria surfaces with 30% Ce3+ ions on (111) planes exhibit higher polishing efficiency, attributed to increased Si-O-Ce bond formation. The simultaneous presence of oxygen vacancies and various acidic and basic sites on ceria surfaces enhances the polishing efficiency, involving acid-base reactions with silica. Defective surfaces show superior efficiency by removing silicate chains, contrasting with nondefective surfaces removing isolated orthosilicate units. This study provides insights into optimizing CMP processes for high-precision glass industry surface finishing.