A novel efficient and entirely green hybrid energy conversion system comprising compressed air energy storage and Kalina KCS11 is proposed for peak shaving application and grid stability. The use of high-temperature thermal energy storage as a replacement for the traditional combustion chamber and a Kalina KCS11 with clean working fluid aims to minimize greenhouse gas emissions while adequately addressing intermittency and electricity curtailment of power grids with high penetration of renewable sources. The proposed system is comprehensively analyzed from the energy, exergy, and economic viewpoints. The thermodynamic simulation results indicate that the air turbine and pressure regulating valve have, respectively, 595.5 and 477.5 kW exergy destruction, accounting for around 40% of total exergy destruction. In addition, employing a KCS11 cycle recovers 57.95% of the heat dissipated in the CAES outlet. Accordingly, the proposed hybrid CAES-KCS11 system has round trip energetic and exergetic efficiencies of 52.97% and 46.28%, respectively. The economic analysis reveals that along with environmental benefits, it has a reasonable payback time of around 3.69 years. Moreover, a total benefit of 740 000 $ is gained during the service year of the system. The hybrid system is found to be more efficient compared to a standalone high-temperature hybrid CAES system.