Polyvinyl alcohol (PVA) electrospun mats with antioxidant activity (PVA/Ros) were obtained by incorporating rosemary extract (RE) into the electrospinning precursor solution. RE compounds interact with PVA, favoring the retention of polyphenols (88 +/- 2%), and improving its thermal stability. The components extracted from PVA/Ros mat were the same as those of the RE. PVA/Ros mats showed a polyphenol content of (15.4 +/- 0.5) mg gallic acid equivalent/g of mat (mg GAE/g) and achieved an antioxidant activity of (120 +/- 8) mu moles Trolox equivalent/g of mat (mu mol TE/g), as measured by Folin-Ciocalteu method and DPPH% assay. The release rate of rosemary polyphenols to several food simulants was measured and kinetic data was adjusted by Fick's diffusion law, Power Law, and Weibull model. The resulting parameters suggested that polymer chain relaxation is the leading mechanism in hydrophilic simulant, while an anomalous release occurred in acid medium. A burst release was observed in lipophilic food simulant, limiting its effectiveness over time. This work shows the potential application of PVA/Ros mats as active food packaging, particularly for hydrophilic and acid food products.