HM-531 was used to modify the hydrophilicity of PCL, and the influences of its content on the melt index, contact angle and tensile properties of the blend system were studied. The influences of voltage, driving air pressure and nozzle height on the microstructure and contact angle of the fiber membrane were explored using a melt electrospinning three-dimensional, and the best process parameters were screened. The results showed that with the increase in HM-531 content, the melt index of the blend increased, and the contact angle decreased continuously. When the content of HM-531 was of a mass fraction of 3%, the MFR of the blend was 9.1 g/10 min, with an increase of 89.6% compared to that of not being added. The contact angle was reduced from 72.92° to 10.22°, and the hydrophilic properties were significantly improved. The tensile strength and elongation at break of the blend showed a trend of first increasing and then decreasing. When the mass fraction of HM-531 was 3%, the tensile strength and the elongation at break reached the maximum, which were 26.8 MPa and 1338.5% respectively. Under the conditions of a voltage of 20 kV, an air pressure of 0.08 MPa and a nozzle height of 5 cm, the fiber diameter of the melt electrospun membrane was the most uniform and the contact angle was 10.52°. The melt electrospun membrane was characterized with uniform fiber size, good appearance and excellent hydrophilic performance, which had good application prospects in the fields of modified atmosphere packaging cling film and rapid drug release film.