Nowadays, the increasing demand to reduce energy consumption and improve process reliability requires an alternative lubricant with an effective tribological performance and environmentally friendly properties to replace traditional lubricants in hot steel manufacturing. The current work reviews recent comprehensive experimental and theoretical investigations in a new generation of alkaline-based glass lubricants, with phosphate, borate, and silicate being intensively researched. This class of lubricants showed an outstanding friction reduction, anti-wear, and anti-oxidation performance on coupled steel pairs over a wide range of temperatures (from 650 °C to 1000 °C). Each type had different tribochemical reactions within itself and with oxidized steel surfaces, which were largely determined by their chemical nature. In addition, the critical role of each structural component was also determined and corroborated by computational simulation. The theoretical studies at quantum and atomic levels reinforced our experimental findings by providing insights into the reaction mechanism using the static and dynamic simulations of the adsorption of lubricant molecules onto iron oxide surfaces. Additionally, the new reactive molecular dynamics (MD) model developed for alkali phosphate will need to be extended further to consider the realistic operating conditions of these lubricants at the atomic scale.