Reactive molecular dynamics simulations have been used to simulate the chemical mechanical polishing (CMP) process of silica glass surfaces with the ceria (111) and (100) surfaces, which are predominantly found in ceria nanoparticles. Since it is known that an alteration layer is formed at the glass surface as a consequence of the chemical interactions with the slurry solutions used for polishing, we have created several glass surface models with different degrees of hydroxylation and porosity for investigating their morphology and chemistry after the interaction with acidic, neutral, and basic water solutions and the ceria surfaces. Both the chemical and mechanical effects under different pressure and temperature conditions have been studied and clarified. According to the simulation results, we have found that the silica slab with a higher degree of hydroxylation (thicker alteration layer) is more reactive, suggesting that proper chemical treatment is fundamental to augment the polishing efficiency. The reactivity between the silica and ceria (111) surfaces is higher at neutral pH since more OH groups present at the two surfaces increased the Si-O-Ce bonds formed at the interface. Usually, an outermost tetrahedral silicate unit connected to the rest of the silicate network through a single bond was removed during the polishing simulations. We observed that higher pressure and temperature accelerated the removal of more SiO4 units. However, excessively high pressure was found to be detrimental since the heterogeneous detachment of SiO4 units led to rougher surfaces and breakage of the Si-O-Si bond, even in the bulk of the glass. Despite the lower concentration of Ce ions at the surface resulting in the lower amount of Si-O-Ce formed, the (100) ceria surface was intrinsically more reactive than (111). The different atomic-scale mechanisms of silica removal at the two ceria surfaces were described and discussed.