A packaging process and structure of electronic device provides first a substrate having a carrying surface and a mounting surface wherein the carrying surface is divided into a device disposing region and a device peripheral region. Then a hydrophobic Fluorine-containing layer is formed in the device peripheral region of the substrate. Subsequently, an electronic device is attached in the device disposing region and is electrically connected to the substrate. Then, a molding compound is employed to encapsulate the electronic device. The bondability between the hydrophobic Fluorine-containing layer and the molding compound is weaker than the bondability between the molding compound and the substrate. Finally, a degating process is performed to remove the excess molding compound positioned at the hydrophobic Fluorine-containing layer to accomplish the packaging process of the electronic device.