Polyhydroxyalkanoates (PHA) is a carbon neutral material that contributes to reducing greenhouse gas emissions due to manufactured from biomass and easily degraded by the enzymatic effects of microorganisms in the natural environment. However, PHA exhibits poorer mechanical properties and processability compared with petroleum‐based plastics. This study used cellulose nanofiber (CNF) to improve limit of PHA. Moreover, CNF was silylated to reduce polarity difference with PHA and enhance the dispersibility of nanocellulose at PHA. At a result, the silylation process was successfully performed by Si‐CH3 stretching peaks in Fourier transform infrared spectroscopy spectra and hydrophobicity of TEOS‐MTES‐CNF (TECNF) was confirmed by observed water contact angle (147°). In addition, nanostructure of TECNF was maintained during silylation and drying process through field emission scanning electron microscopy. Moreover, the PHA/TECNF composite showed enhanced processability, and tensile strength was increase almost 37% (0.52 MPa) compared with PHA. Oxygen transmission rates (300 cc/m2۰day) and single lap shear strength (225 kPa) were determined to be at least equivalent or superior to those of commercial packaging materials. Therefore, TECNF could be considered as a reinforcing agent, nucleating agent, and plasticizer in PHA. Also, this composite has possibilities to using as environmentally friendly packaging materials.