This study investigates the sustainable use of Eucalyptus spp. bark through different chemical (hydrothermal, acid, alkaline, and bleaching) and physical (milling) pretreatments in the production of sustainable films. Valorization of agro-industrial residues and the demand for sustainable materials pose challenges for environmentally responsible solutions. Eucalyptus spp. bark, rich in cellulose, hemicellulose, and lignin, is a promising source for creating sustainable materials like films. In this study, the use of chemical and physical treatments aims to optimize biomass extraction and improve the chemical, thermal, mechanical, and optical properties of the films. The films showed an excellent light barrier capacity, with a transmittance below 1%. Crystallinity indices varied with the pretreatment: 8.15% for hydrothermal, 7.01% for alkaline, 7.63% for acid, and 10.80% for bleaching. The highest crystallinity value was obtained through bleaching, by removing amorphous components like lignin and hemicellulose. The alkaline pretreatment yielded stronger films (maximum stress of 8.8 MPa, Young’s modulus of 331.3 MPa) owing to the retained lignin and the hemicellulose reinforcing the material. This study contributes to the field of sustainable development by converting residues into valuable materials and by advancing the circular economy. The films’ specific properties make them suitable for applications like sustainable packaging, addressing environmental and industrial challenges.