In our previous work, we found that the (104) and (012) surfaces are more prone to O2 release. Ab-initio molecular dynamics (AIMD) results show that the under-coordinated oxygen atoms from the delithiated structures can combine and eventually evolve as O2. Thus, the intrinsic surface properties of cathodes and the interfacial interactions between cathode and electrolyte need to be considered to enhance the cathode stability. The surface engineering and design of the electrode material have been proposed as a promising path to achieving safe and high-voltage cathodes for LiBs. In this work, firstly we report the stability, interfacial chemistry, oxidation-reduction behavior and surface thermodynamics of the major surfaces of LiCoO2 based on the calculations obtained with the density functional theory (DFT) approach. Further, we present the results achieved from DFT-based calculations and experimental techniques (e.g. electrochemical cycling, in-situ heating transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Raman characterizations) on the surface coating approach to enhance the structural stability of LiCoO2 by providing a physical barrier for oxygen evolution. Our experimental work shows that the coated sample could exhibit more than 75% capacity retention after 40 cycles while the pristine sample failed after 20 cycles with the same condition. Our computations suggest that the interaction between the physical barrier and the electrode’s surface leads to an interfacial chemical bonding that prevents O2 evolution. Overall, we expect that this combined approach will allow improving the overall performance of the battery by addressing the multifaceted problems that play a role in the safety problems of cathodes.