Resveratrol is known for its health benefits. However, it lacks efficacy in vivo due to low solubility and stability, limiting its bioavailability. The objective of this study was to develop an effective nanofibrous oral delivery system for resveratrol to improve its bioaccessibility using controlled release. Resveratrol (at different concentrations 2, 5 and 10% w/w) loaded zein nanofibers were prepared using the electrospinning technique. Zein nanofibers with ribbon-like morphology with an average fiber diameter of 404 nm, higher encapsulation efficiency up to 96.9% and 66.2% radical scavenging activity were fabricated. The transition of the crystallinity of resveratrol to amorphous form was confirmed from the thermal analysis. Resveratrol release controlled by diffusion and the relaxational contribution from the zein carrier was observed using Peppas Sahlin kinetics. The release profile of resveratrol from nanofibers with in vitro simulated gastrointestinal condition showed effective protection of encapsulated resveratrol with gastric conditions and controlled release with the intestinal conditions. Improved bioaccessibility up to 67.6% of encapsulated resveratrol was achieved, while native resveratrol was only about 48.1%. Its potential as a nanostructured edible coating on minimally processed foods was evaluated by direct electrospinning of resveratrol loaded zein nanofibers on cut apple slices. Nanocoating effectively controlled moisture loss and retained the color of apple slices over the study period of 6 h.