Cations such as Lewis acids have been shown to enhance the catalytic activity of high-valent Fe−oxygen intermediates. Herein, we present a pyridine diamine ethylene glycol macrocycle, which can form Zn(II)-or Fe(III)-complex with the NNN site, while allowing redox-inactive cations to bind to the ethylene glycol moiety. The addition of alkali, alkali earth, and lanthanum ions resulted in positive shifts to the Fe(III/II) redox potential. Calculation of dissociation constants showed the tightest binding with a Ba 2+ ion. Density functional theory calculations were used to elucidate the effects of redox inactive cations toward the electronic structures of Fe complexes. Although the Fe−NNN complexes, both in the absence and presence of cations, can catalyze C−H oxidation of 9,10-dihydroanthracene, to give anthracene [hydrogen atom transfer (HAT) product], anthrone, and anthraquinone [oxygen atom transfer (OAT) products], highest overall activity and OAT/HAT product ratios were obtained in the presence of dications, that is, Ba 2+ and Mg 2+ , respectively.