The activation of methane at ambient conditions and its conversion into more valuable feedstocks is a challenge for future, because it would permit a much more efficient use of methane from either geological deposits or biogenic sources.[1] Most low-temperature routes for the activation of methane are based on transition-metal catalysts, and particularly promising approaches involve the functionalization of methane with the aid of platinum complexes.[2] While these systems achieve the activation of methane under comparably mild conditions, they are far removed from possible future applications in large-scale processes because of the expensive catalysts or because of the nature of the products.[3] A promising catalyst for the low-temperature activation of methane is Li+ ion doped magnesium oxide, although this still needs considerable improvement before large-scale applications would be feasible.[1, 4] This improvement is the point where basic research can complement applied science by means of providing a more detailed understanding of the underlying elementary steps at a molecular level. Accordingly, the reactions of diatomic MgO as well as several model clusters have been studied extensively by means of theory.[5–9] Theory strongly suggests that the cationic species [MgO]+ should effectively activate methane,[10, 11] and also for neutral MgO the computed activation barrier is rather low.[9] Accordingly, the elementary steps in the chemistry of magnesium and its oxides have received considerable attention in several experimental studies,[12–19] yet a decisive route for the generation of ionic species such as [MgO]+ in amounts