The invention relates to a preparation method and an application of high expansion coefficient copper sealing glass powder, wherein the technical difficult problems of high cost, long production period, high use environment requirements and the like of the existing copper seal electrical connector are solved. The high expansion coefficient copper sealing glass powder adopts a phosphate glass system and comprises the following components by mole: 45-65% of P205, 10-15% of B203, 4-15% of Al2O3, 5-20% of Na2O, 8-22% of K2O, and 0-12% of PbO+BaO+CaO+MgO. The application comprises: carrying out mixing, heating, stirring, molding, drying and other steps on the glass powder and a paraffin thin sheet, assembling a sealing copper shell and a glass billet, placing on a graphite mold, placing into a nitrogen atmosphere furnace or vacuum furnace, carrying out thermal insulation for 30 min at a temperature of 600-780 DEG C, and cooling to a room temperature to obtain the electrical connector with characteristics of high temperature resistance, high resistivity and high air-tightness. According to the present invention, the glass powder can match to the copper alloy shell expansion coefficient, the produced copper alloy electrical connector can achieve good electrical property, the preparation method is suitable for industrial production, and the economic benefits can be increased.