In this paper, nano/microfibrils were applied to enhance the mechanical and hydrophobic properties of the sugarcane bagasse fiber films. The successful preparation of nano/microfibrils was confirmed by scanning electron microscope (SEM), X-ray diffraction (XRD), fiber length analyzer (FLA), and ion chromatography (IC). The transparency, morphology, mechanical and hydrophobic properties of the cellulose films were evaluated. The results show that the nanoparticle was formed by the hemicellulose diffusing on the surface of the cellulose and agglomerating in the film-forming process at 40 °C. The elastic modulus of the cellulose film was as high as 4140.60 MPa, and the water contact angle was increased to 113°. The micro/nanostructures were formed due to hemicellulose adsorption on nano/microfilament surfaces. The hydrophobicity of the films was improved. The directional crystallization of nano/microfibrous molecules was found. Cellulose films with a high elastic modulus and high elasticity were obtained. It provides theoretical support for the preparation of high-performance cellulose film.