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High-temperature proton-exchange membrane fuel cells (HT-PEMFCs) have indeed emerged as highly efficient devices for energy conversion with numerous applications, ranging from portable electronics to transportation. The development of advanced electrolyte materials is imperative to enhance the PEMFCs’ stability and performance. Herein, we use sulfonated polyvinyl chloride (SPVC) and 2,5-benzimidazole-modified montmorillonite (AB-MMT) to create a series of novel composite electrolytes for PEMFC via a solution-casting method. PVC, well known for its excellent film-forming properties, is combined with modified MMT, a natural inorganic clay with a high surface area and ion-exchange capability (IEC). The composite polymer electrolyte membranes (PEMs) are further doped with phosphoric acid (PA) at varying concentrations. The structural, morphological, and electrochemical properties of prepared …