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Nafion membranes are widely used as proton exchange membranes, but their proton conductivity deteriorates in high-temperature environments due to the loss of water molecules. To address this challenge, we propose the utilization of porous aromatic frameworks (PAFs) as a potential solution. PAFs exhibit remarkable characteristics, such as a high specific surface area and porosity, and their porous channels can be post-synthesized. Here, a novel approach was employed to synthesize a PAF material, designated as PAF-45D, which exhibits a specific surface area of 1571.9 m2·g−1 and possesses the added benefits of facile synthesis and a low cost. Subsequently, sulfonation treatment was applied to PAF-45D in order to introduce sulfonic acid groups into its pores, resulting in the formation of PAF-45DS. The successful incorporation of sulfonic groups was confirmed through TG, IR, and EDS analyses. Furthermore, a novel Nafion composite membrane was prepared by incorporating PAF-45DS. The Nyquist plot of the composite membranes demonstrates that the sulfonated PAF-45DS material can enhance the proton conductivity of Nafion membranes at high temperatures. Specifically, under identical film formation conditions, doping with a 4% mass fraction of PAF-45DS, the conductivity of the Nafion composite membrane increased remarkably from 2.25 × 10−3 S·cm−1 to 5.67 × 10−3 S·cm−1, nearly 2.5 times higher. Such promising and cost-effective materials could be envisioned for application in the field of Nafion composite membranes. [ABSTRACT FROM AUTHOR]