Poly(vinyl alcohol) (PVA) hydrogel nanofibers are a potential candidate for textile-based drug-release applications. Polycarboxylic acids 1,2,3,4-butanetetracarboxylic acid (BTCA) and citric acid (CA) are low-cost alternatives reported to easily crosslink electrospun PVA hydrogel. These can be directly added into the spinning solutions. One of the most efficient non-steroidal anti-inflammatory drugs (NSAIDs), Naproxen (NAP), was selected as a model drug for this study. The release mechanisms of drug-loaded electrospun PVA nanofibers are based on the diffusion of the drugs through the swollen PVA fibrous matrix and the release due to partial dissolution of the matrix. Control over drug-release characteristics can be provided through partial crosslinking of the PVA fibrous matrix.