Polymer electrolyte membranes in which the hydrophilic and hydrophobic domains phase separate exhibit improved properties and stability. Such a phase separation of hydrophilic and hydrophobic domains can be achieved by polymerizing a 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide-bisphenol A (DOPO-BPA) and 1,4-bis(4-fluorobenzoyl)benzene (1,4-FBB) monomer. In this work, sulfonated polymer membranes with various degrees of sulfonation (DS) were prepared and their physicochemical and electrochemical properties were studied. In addition, the effect of molecular structure on the durability of the copolymers was investigated. The sulfonated copolymers were characterized by Fourier-transform infrared spectroscopy and proton nuclear magnetic resonance spectroscopy. Then, sulfonated membranes were prepared using these copolymers by the solvent casting method, and their morphologies were investigated by atomic force microscopy. The effect of DS on the thermal, mechanical, and oxidative stabilities, water uptake behavior, and ion-exchange capacity of the membranes was determined. The results showed that compared with the commercially available Nafion 212 polymer electrolyte membrane, the electrolyte membrane based on DOPO-BPA and 1,4-FBB exhibited a lower water uptake and excellent dimensional stability despite having a relatively high ion-exchange capacity. The low water uptake is an important characteristic that ensures the stability of the polymer electrolyte membrane in fuel cell applications.