In the view of physiological significance, the transition-metal-mediated routes for nitrite (NO2-) to nitric oxide (NO) conversion and phenol oxidation are of prime importance. Probing the reactivity of substituted phenols toward the nitritocopper(II) cryptate complex [mC]Cu(kappa(2)-O2N)(ClO4) (1a), this report illustrates NO release from nitrite at copper(II) following a protoncoupled electron transfer (PCET) pathway. Moreover, a different protonated state of la with a proton hosted in the outer coordination sphere, [mCH]Cu(kappa(2)-O2N)(ClO4)(2 )(3), also reacts with substituted phenols via primary electron transfer from the phenol. Intriguingly, the alternative mechanism operative because of the presence of a proton at the remote site in 3 facilitates an unusual anaerobic pathway for phenol nitration.