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Nafion has been dominating the proton exchange membrane (PEM) market because of its adequacy for the proton exchange operation. However, because of its high cost, low performance at low relative humidity, and finally environmental unfriendliness, researchers have been developing and working on Nafion alternatives. In this review, we assess how biopolymers present an opportunity as an eco‐friendly material able to replace the conventional Nafion membrane in proton exchange membrane fuel cells (PEMFC). Chitosan and cellulose were the most studied in literature owing to their abundance in nature, low cost, and high affinity for water, which are sought‐after properties for PEM. In addition to that, their ease of modification through their hydroxyl or amine groups represents an opportunity to further enhance their characteristics and thus meet the criteria of diverse applications. The use of biopolymers as an adequate PEM is facing many challenges. Having a practical proton conductivity and securing the physicochemical stability of the biopolymers in fuel cell operating conditions are two of the most important challenges to overcome. Promising strategies to simultaneously address these challenges such as crosslinking, making interpenetrated networks, and making blends and composites are reported. [ABSTRACT FROM AUTHOR]