Interface engineering is essential for cellulosic fiber-reinforced polymer composites to achieve high strength and toughness. In this study, carboxymethyl cellulose (CMC) functionalized with hydrophobic quaternary ammonium ions (QAs) were utilized to modify the interface between holocellulose fibers (HF) and acrylic resin. The wet HF/CMC papers were prepared by vacuum filtration, akin to papermaking, followed by cationic ion exchange with different hydrophobic QAs. Subsequently, the modified papers were dried, impregnated with an acrylic resin monomer, and cured to produce transparent composite films. The effect of the hydrophobic QA moieties on the structure and optical and mechanical properties of the HF/CMC/acrylic resin composites were investigated. The composite film with cetyltrimethylammonium (CTA)-functionalized CMC showed high optical transmittance (87%) with low haze (43%), while the composite film with phenyltrimethylammonium (PTMA)-functionalized CMC demonstrated high Young’s modulus of 7.6 GPa and high tensile strength of 180 MPa. These properties are higher than those of the composites prepared through covalent interfacial modification strategies. The results highlighted the crucial role of hydrophobic functionalized CMCs in facilitating homogeneous resin impregnation in the HF fiber network, producing a composite with enhanced interfacial adhesion strength, increased optical transparency, and mechanical strength. This facile use of hydrophobic CMCs as interfacial compatibilizers provides an energy-efficient route for preparing transparent, thin, and flexible composite films favorable in optoelectronic applications.