Low cost membrane electrode assemblies (MEA) with improved coulombic efficiency (CE), reduced maintenance cost, and improved deliverable capacity have been developed for redox flow batteries and other electrochemical reaction applications. The MEA comprises: a microporous substrate membrane, first and second hydrophilic ionomeric polymer coating layers on surfaces of the microporous substrate membrane, and an electrode adhered to a second surface of the second hydrophilic ionomeric polymer coating layer. Methods of preparing the MEA and a redox flow battery system incorporating the MEA are also described.