Metal-phenolic networks (MPNs) are a versatile class of organic-inorganic hybrid systems that are generating interest for applications in catalysis, bioimaging, and drug delivery. These self-assembled MPNs possess metal-coordinated structures and may potentially serve as redox-responsive platforms for triggered disassembly or drug release. Therefore, a comprehensive study of the reduction and oxidation behavior of MPNs for evaluating their redox responsiveness, specific conditions required for their disassembly, and the kinetics of metal ion release, is necessary. Using a representative MPN gallic acid-iron (GA/Fe) system, we conducted electrochemical studies to provide fundamental insights into the redox behavior of these MPNs. We demonstrate that GA/Fe is redox active, and evaluate its electrochemical reversibility, identify the oxidation state of the redox-active species, and provide information regarding the stability of the networks toward reductive stimuli and specific redox conditions required for the "on-off" or continuous release of Fe. Overall, through studying the redox properties of GA/Fe films, we advance the understanding of multifunctional iron-containing MPN platforms that may have practical significance for biologically relevant applications.