Recovering alkali from Bayer red mud is crucial for storage security, resource utilization and environmental protection. In this study, the addition of MgO and/or CaO was conducted to recover alkali from red mud with a hydrothermal method for the first time. A synergistic result with a residual Na₂O/SiO₂ weight ratio of 0.03 was obtained by adding the blend of CaO and MgO at an appropriate temperature. MgO was found to be more temperature-dependent than CaO when substituting Na₂O from red mud due to their different hydration processes. The alkali recovery was controlled by a reaction at a temperature of <200 °C and by internal diffusion at a higher temperature for MgO, but controlled by internal diffusion for CaO in the whole temperature range studied. The formation of hydrotalcite-like compounds with a loose structure was verified with the help of XRD, FTIR, and SEM-EDS. It was proved that both the reaction kinetics and the characteristics of solid products have a significant influence on the recovery of alkali.