This study reports on the effect of organic polyvinyl alcohol (PVA) and silica matrix on the properties of cellulose-based nanocomposites. Nanofibrillated cellulose was isolated from kraft pulp and treated with Pulpzyme HC 2500 enzyme prior to high-pressure homogenization in order to lower energy consumption. Three nanocomposite films were fabricated via the casting process: nanofibrillated cellulose, nanocellulose-PVA (NC-PVA) and nanocellulose-silica (NC-Si). Chemical characterization and crystallization were determined with FTIR. Thermal stability was investigated with thermogravimetric analysis. Morphological alterations were monitored with scanning electron microscopy. A universal testing machine and dynamic mechanical thermal analysis were used for determination of Young's and storage moduli. The real and imaginary parts of permittivity and electric modulus were evaluated using an impedance analyzer. Considerable alterations were seen under FTIR. Thermal stability was lower in NC-Si than in NC-PVA due to lower crystallinity. Higher Young's modulus and storage moduli were observed in NC-PVA than in NC-Si. NC-PVA exhibited a singular relaxation process, while a double relaxation process was seen in NC-Si. Consequently, the nanocomposite film prepared from the organic matrix (NC-PVA) had a mechanical advantage for industrial applications. However, neat NC composite revealed the highest storage modulus and thermal stability.