The Cover Feature shows that the Cu(II) bis‐oxamidate complex undergoes selective water oxidation to release dioxygen through the single‐electron transfer water nucleophilic attack (SET‐WNA) pathway, while the Ni(II) bis‐oxamidate complex shows competition between water oxidation and molecular species deactivation following the proton transfer water electrophilic attack (PT‐WEA) pathway, ultimately leading to decomposition to NiOx. Extensive computational studies with density functional theory (DFT) show that the 2e− oxidized anionic intermediate [(L1•)NiIII(OH)]1− in the nickel complex promotes both nucleophilic (OH−) and electrophilic (H+) attack, while the corresponding copper intermediate, [(L1•)CuII(OH•)]1−, displays radical character on the hydroxyl ligand, thus prohibiting catalyst degradation. More information can be found in the Research Article by A. K. Singh and L. Roy.