The proanthocyanidins encapsulated in zein (zein-PA) fibers was via electrospinning technique. The kinetics and antioxidant capacity of PA from zein fibers was investigated by cyclic voltammetry. Circular dichroism was used to investigate the secondary structure change of zein and its influence on the shape of fibers. The addition of PA caused a significant increase in viscosity and made fibers wider. These hydrogen bonds between zein and PA molecules would favor the a-helix change and decrease the beta-folds of zein in electrospinning solutions, leading to a round-shaped tendency of fibers and enhancing the thermal properties slightly. Zein-PA fibers showed high encapsulation efficiency dose to 100%, and the encapsulated PA retained its antioxidant capacity in fibers. Zein-PA fibers showed a good controlled release toward PA, and, the predominant release of PA from fibers was Fickian diffusion, which could be well described by first-order model and Hixson-Crowell model.