We report electrochemical generation of a stable Rh(II) porphyrin (Rh-II(F28TPP)) from a four-coordinate Rh(l) precursor [Rh-I (F28TPP)](-) dissolved in weakly coordinating electrolyte solutions. This work provides the first example of an unambiguously reversible one-electron electrochemical oxidation of a Rh-I(por), and demonstrates that electrochemical oxidation can be performed under conditions that are compatible with alkane activation. These studies begin to classify those media capable of supporting a stable Rh-II(por), and those that induce disproportionation.