The long-term stability of cathode materials is another crucial factor that deters the wide applicability of DRX materials for water splitting reactions. We, therefore, investigated the stability in 1M KOH. The chronopotentiometry results suggest that 2 has superb stability of more than 5.5 days and even beyond without an appreciable increment in overpotential (Figure ). In contrast, 1 shows a tendency to increase in potential even after a few hours. This superb stability of 2 is attributed to the following factors. The Na doping in the lattice increased the oxidation states of Ru and Ni, thereby modifying the electronic structures. As reported earlier, higher oxidation states of TMs in layered structure are beneficial for OER. Additionally, these higher oxidation states can be easily stabilized in DRX layered structures, which is essential for sustained OER reactions. Furthermore, it has also been widely accepted that high-valence transition metal cations facilitate the adsorption of OH-with the catalysts to form adsorbed -OOH species to promote OER reaction steps readily. The above results reveal the enhanced electrochemical performance of 2 compared to not only 1 but also to many other cathode materials (Figure ). It is generally assumed that the oxygen BE at the surface largely influences the OER activity. For this, a series of DFT calculations were conducted to investigate the role of Nadoping on surface oxygen atoms as shown in Figure . The favorable locations of Ni and Na in 2 are found with Genetics Algorithm (GA). DFT calculations established that while Ni atoms prefer to occupy the Ru layer (Figure ), Na atoms prefer to locate in Li layer (Figure ). Surprisingly, the average oxygen Bes in both cases are almost same (∼7 eV), but while it is almost uniform in 1, but 2 shows higher fluctuations. In particular, the lowest BE for oxygen is 5.45 eV in 2 and 6.51 eV in 1. The Na-substitution promotes the OER activity by reducing the BE of some oxygen atoms at the surface and accentuating the facile diffusion of O2 gas, which is consistent with experimental results. The total density of states (DOS) reveals that the electrons' occupancy near the Fermi level between 1 and 2 is different. In addition, the projected DOS of oxygen 2p orbital in 2 (Figure ) is substantially different from that in 1 (Figure ) and shows a shift in O p-band center toward the Fermi level , which leads to better TM-O overlap and creates reduced charge transfer resistance well supported with Figure . In summary, we have enrooted the idea of engaging cation disordered cathode materials for OER application synthesized by a facile solid-state route. Na-doping in 2 solved the issue of instability prevailing in disordered cathodes but also contradicted the former idea that layered structures alone can stabilize TM oxidized species for improved OER performances. Nonetheless, 2 performs much better than 1 and many other layered cathode materials, including dedicated OER electrocatalysts. 2 requires a low η of 270/390 mV to display current densities of 10/250 mA cm -2 and demonstrate superb stability for more than 5.5 days, which is exceptionally better than many of the OER electrocatalysts reported to date. The significant enhancement in the OER performance is attributed to several intriguing factors. First, the disordered structure provides better interaction between Li and TMs, often unavailable in layered cathodes where Li and TMs occupy a fixed position. Secondly, the induction of Na + promoted the oxidation state of TMs (Ni and Ru), favoring OER kinetics. Thirdly, DFT calculations predicted that Na + accentuates the facile evolution of O2 from the surface layer, thereby alleviating the sluggish reaction kinetics often observed in the OER. We believe that our finding of engaging DRX cathode materials for the OER application will pave a novel design strategy for future materials of this family for high-performance electrocatalysts for energy conversion reactions.