Regenerated cellulose packaging materials can alleviate the environmental pollution and carbon emissions caused by conventional plastics and other chemicals. They require regenerated cellulose films with good barrier properties, such as strong water resistance. Herein, using an environmentally friendly solvent at room temperature, a straightforward procedure for synthesizing these regenerated cellulose (RC) films, with excellent barrier properties and doping with nano-SiO₂, is presented. After the surface silanization modification, the obtained nanocomposite films exhibited a hydrophobic surface (HRC), in which the nano-SiO₂ provided a high mechanical strength, whereas octadecyltrichlorosilane (OTS) provided hydrophobic long-chain alkanes. The contents of the nano-SiO₂ and the concentrations of the OTS/n-hexane in regenerated cellulose composite films are crucial, as they define its morphological structure, tensile strength, UV-shielding ability, and the other performance of these composite films. When the nano-SiO₂ content was 6%, the tensile stress of the composite film (RC6) increased by 41.2%, the maximum tensile stress was 77.22 MPa, and the strain-at-break was 14%. Meanwhile, the HRC films had more superior multifunctional integrations of tensile strength (73.91 MPa), hydrophobicity (HRC WCA = 143.8°), UV resistance (>95%), and oxygen barrier properties (5.41 × 10⁻¹¹ mL·cm/m²·s·Pa) than the previously reported regenerated cellulose films in packaging materials. Moreover, the modified regenerated cellulose films could biodegrade entirely in soil. These results provide an experimental basis for preparing regenerated-cellulose-based nanocomposite films that exhibit a high performance in packaging applications.