Driven by the escalating environmental impact of synthetic materials, there has been a growing focus on employing eco‐sustainable biomass‐derived biopolymers and native materials as a viable alternative to traditional energy storage applications. Biopolymer‐based energy devices, like batteries, supercapacitors, electrode materials, and ion‐exchange membranes, a novel and eco‐conscious approach, hold great potential for flexible and smart electrochemical energy storage and conversion devices, owing to their affordability, environmental sustainability, and biodegradability. This critical review outlines the sources and properties of biopolymers leading to energy storage and emphasizes their utilization in the energy sector. Despite their inherent constraints, biopolymers can be effectively leveraged when combined with other materials in composites. This collaborative approach not only refines their intrinsic physical attributes but also elevates the electrochemical performance of biologically active molecules. In this regard, bionanocomposites, a class of materials combining biopolymers and nanoparticles, have emerged as a promising greener alternative to conventional petroleum‐based polymers. Their biocompatibility, biodegradability, and antimicrobial properties have promoted their increased commercialization, thus paving the way for a more sustainable future. The review concludes by identifying and effectively addressing the limitations, challenges, and future perspectives of biopolymers in energy storage applications.