Hydrolysis in alkali-doped aluminosilicate glasses is one of the most complicated mechanisms in glass science. There remain many fundamental and unresolved issues with implications on their potential applications. Herein, we address this challenge by carrying out detailed calculations on the structure and properties of both anhydrate (dry) and hydrated alkali aluminosilicate glasses on carefully constructed models. Specifically, the Na-, (Na + K)-, and K-doped aluminosilicate glasses with compositions (SiO2)(0.6)(Al2O3)(0.2)(Na2O)(0.2) (-) (x)(K2O)(x) (x = 0, 0.10, and 0.20) are simulated using ab initio molecular dynamics (AIMD). The local short- and intermediate-range order in these glasses is analyzed in terms of atomic pair distribution, coordination number, bond length, and bond angle distributions to delineate the subtle variations due to different alkali sizes and hydrolysis. The electronic structure, interatomic bonding, mechanical, and optical properties for these models are calculated and validated with available experimental data. We use the novel concept of total bond order density (TBOD), the quantum mechanically derived metric, to characterize the internal cohesion and strength in the simulated glasses. Detailed analysis of the hydrolysis mechanism enables us to provide information on the complex interplay of various participating elements and their interactions at the atomic level. Such detailed information provides a new platform of knowledge, which is crucial for understanding the issues related to glass corrosion and durability, and ways and means for their special applications in commercial glass products. Both undissociated molecular water and dissociated water in the form of hydroxyl groups exist in the hydrated models in the presence of alkali ions. For the first time, we observed the opposite mixed alkali effect in the Poisson's ratio for anhydrate and hydrated glasses.