Polymer electrolyte membranes have found broad application in a number of processes, being fuel cells, due to energy concerns, the main focus of the scientific community worldwide. Relatively little attention has been paid to the use of these materials in electrochemical production and separation processes. In this review, we put emphasis upon the application of Nafion membranes in electrochemical membrane reactors for chlorine recycling. The performance of such electrochemical reactors can be influenced by a number of factors including the properties of the membrane, which play an important role in reactor optimization. This review discusses the role of Nafion as a membrane, as well as its importance in the catalyst layer for the formation of the so-called three-phase boundary. The influence of an equilibrated medium on the Nafion proton conductivity and Cl− crossover, as well as the influence of the catalyst ink dispersion medium on the Nafion/catalyst self-assembly and its importance for the formation of an ionic conducting network in the catalyst layer are summarized.