Reductive activation of O is achieved by using the [Fe(FTPP)Cl] (FTPP = 5,10,15,20-tetrakis(pentafluorophenyl) porphyrinate) porphyrin through electrochemical reduction of the [Fe(FTPP)(O)] superoxo complex. Formation of the [Fe(FTPP)(OO)] peroxo species is monitored by using low-temperature electronic absorption spectroscopy, electron paramagnetic resonance, and cyclic voltammetry. Its subsequent protonation to yield the [Fe(FTPP)(OOH)] hydroperoxo intermediate is probed using low-temperature electronic absorption spectroscopy and electron paramagnetic resonance.