Biodegradable polymers hold great therapeutic value, especially through the addition of additives for controlled drug release. Nanocellulose has shown promise in drug delivery, yet usually requires chemical crosslinking with harsh acids and solvents. Nanocellulose fibrils (NFCs) and 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-mediated oxidized nanocellulose fibrils (TNFCs) with poly (vinyl alcohol) (PVA) could be aqueously formulated to control the release of model drug acetaminophen over 144 h. The release was evaluated with a multiphase release mechanism to determine which mechanism(s) contribute to the overall release and to what degree. Doing so indicated that the TNFCs in PVA control the release of acetaminophen more than NFCs in PVA. Modeling showed that this release was mostly due to burst release—drug coming off the immediate surface, rather than diffusing out of the matrix.