The influence of different additives on the oxygen reduction reaction/oxygen evolution reaction (ORR/OER) in magnesium‐containing N ‐butyl‐N ‐methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([BMP][TFSI]) on a glassy carbon electrode was investigated to gain a better understanding of the electrochemical processes in Mg–air batteries. 18‐Crown‐6 was used as a complexing agent for Mg ions to hinder the passivation caused by their reaction with ORR products such as superoxide and peroxide anions. Furthermore, borane dimethylamine complex (NBH) was used as a potential water‐removing agent to inhibit electrode passivation by reacting with trace impurities of water. The electrochemical processes were characterized by differential electrochemical mass spectrometry to monitor the consumed and evolved O2 in the ORR/OER and determine the number of transferred electrons. Crown ether and NBH efficiently masked Mg$^{2+}$. A stochiometric excess of crown ether resulted in reduced formation of a passivation layer, whereas at too high concentrations the reversibility of the ORR/OER was diminished.