widespread adoption and short functional lifetime of traditional energy storage devices will bound to cause global environmental impact (such as e-waste and electronic equipment). [3] Although a large number of studies are reported on novel energy storage devices to tackle this epidemic, such as bio-based hydrogels, [4] film materials. [5] However, hydrogels with conductive nanofiller as energy storage materials are usually made with a tremendous amount of water, [6] and lack integrity and tunability of internal structure and composition, which are generally fragile, mechanically unstable, and poorly water-resistant. [7] Especially, chemical crosslinking and chemical modification methods are commonly required to process polymeric hydrogels, which inevitably suffer from toxic chemicals, complex processing procedures, and high energy consumption. [8] In contrast, film materials are considered to be promising candidates for flexible energy storage materials because of their high conductivity, excellent chemical stability, and excellent merits in energy storage and other applications. [9] To date, methods for preparing film materials, such as vacuumassisted filtration, spin coating, and spray coating, have been developed and shown to have potential applications in fields such as flexible electronics, energy conversion, supercapacitors, and electromagnetic interference shielding. [10] Although film materials may provide outstanding results, most of theseThe development of advanced biomaterial with mechanically robust and high energy density is critical for flexible electronics, such as batteries and supercapacitors. Plant proteins are ideal candidates for making flexible electronics due to their renewable and eco-friendly natures. However, due to the weak intermolecular interactions and abundant hydrophilic groups of protein chains, the mechanical properties of protein-based materials, especially in bulk materials, are largely constrained, which hinders their performance in practical applications. Here, a green and scalable method is shown for the fabrication of advanced film biomaterials with high mechanical strength (36.3 MPa), toughness (21.25 MJ m −3 ), and extraordinary fatigue-resistance (213 000 times) by incorporating tailor-made core-double-shell structured nanoparticles. Subsequently, the film biomaterials combine to construct an ordered, dense bulk material by stacking-up and hot-pressing techniques. Surprisingly, the solidstate supercapacitor based on compacted bulk material shows an ultrahigh energy density of 25.8 Wh kg −1 , which is much higher than those previously reported advanced materials. Notably, the bulk material also demonstrates long-term cycling stability, which can be maintained under ambient condition or immersed in H 2 SO 4 electrolyte for more than 120 days. Thus, this research improves the competitiveness of protein-based materials for real-world applications such as flexible electronics and solid-state supercapacitors.