In the current work, by using various additives, the spray cooling in the transition boiling regime is significantly augmented due to the vapor film instability enhancing, which helps to overcome the disadvantages reported in the open literature for the attainment of high heat flux in the aforesaid boiling regime. Saline water containing dissolved carbon dioxide produces two favorable conditions for high heat transfer rate: (1) controlled vapor bubble nucleation and (2) low entrapped vapor bubbles coalescence rate. These phenomena are the parameters defining the step-up in the heat transfer rate. Systematic spray cooling (from 900 °C) experiments were conducted on a 6-mm thick AISI 304 steel plate (100 mm × 100 mm). The heat transfer analysis indicates that the heat removal rate in case of soda added water depicts an increasing trend with the rising of the soda concentration up to 40% in water, and further increment in soda water concentration declines the heat removal rate due to the formation of the uncontrolled vapor bubbles undergoing early coalescence. In case of salt added carbonated water spray cooling, the quenching performance indicates step-up in critical heat flux up to 1.7 MW/m2. In addition to the above, the spray cooling performance of the above-stated coolant is compared with other potential coolants such as soda–surfactant–water, soda–alcohol–water and soda–salt–surfactant–water mixtures.