This study focused on the fabrication, characterization, and release properties of electrospun tea polyphenol (TPP) loaded porous core-shell structured fibers. The morphology, structure and properties of the electrospun TPP loaded porous core-shell fibers were investigated by a combination of Fourier transformation infrared spectroscopy (FTIR), scanning electron microscopy (SEM), contact angle (CA) measurements, transmission electron microscopy (TEM), etc. In addition, the cumulative drug release rate of TPP loaded porous core-shell fibers was determined by ultraviolet (UV) spectrophotometer, and the release mechanism was investigated using Fickian diffusion equation, which would provide the theoretical basis for future study. The results showed TPP loaded porous core-shell structured fibers were successfully prepared by coaxial electrospinning, and the porous structure of the core-shell fibers could further enlarge the specific surface area, enhance the hydrophobic properties, and improve the drug release properties.