In this work, water-resistant poly (vinyl alcohol) (PVA)/poly (acrylic acid) (PAA) electrospun fibers encapsulating tangeretin (Tan) were fabricated by emulsion-electrospinning. To optimize the electrospinning condition, the size and morphology of electrospun fibers were characterized by dynamic light scattering (DLS), optical light microscope, fluorescence microscopy, and scanning electron microscopy (SEM), respectively. The optimized initial concentration of PVA/PAA was 10% (w/w) with a mass ratio of 3:7. The time and temperature of optimized thermal crosslinking treatment were 2 h and 145 °C, respectively. The results of XRD and SEM showed that the Tan was successfully incorporated into smooth PVA/PAA electrospun fibers and those fibers possessed nano-diameter size and high porosity. The encapsulation of Tan had no significant impact on the antioxidant activity of PVA/PAA/Tan crosslinking electrospun fibers. The in vitro release test showed the PVA/PAA/Tan crosslinking electrospun fibers achieved durable release profiles and lower burst release rates than that from the pure Tan emulsion. Based on these results, it is concluded that PVA/PAA/Tan crosslinking electrospun fibers prepared by emulsion-electrospinning serve as a promising technique in the fields of water-insoluble drug delivery and slow-release.