Poly(arylene ether sulfone)s sulfonated are promising materials for application as proton exchange membranes (PEM) due to their good electrochemical properties. In this study, the synthesis procedure was studied aiming at the production of a new copolymer for use as a PEM. In addition, considering the inefficiency of the recovery route described in the literature, the influence of each monomer in the copolymer recovery from the polymerization solution was evaluated. The monomers were characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Thermogravimetry (TG), confirming their structure and purity. The four copolymers, produced as a result of different monomers' molar ratios, were recovered in different ways. While those with sulfonic groups were recovered with acidic solution, the other polymers without pending sulfonic groups were recovered with deionized water. The copolymers were characterized by FTIR, wherein the copolymers characteristic bands were observed, including those characteristic of diaryl ethers, evidence of the proposed polymerization mechanism.