IIn order to enhance the ignition ability and reliability of traditional electronic initiators, a novel electronic initiator has been designed to integrate with a nanothermite multilayer film and an electrode plug. The Al/CuOx nanothermite multilayer film with different thickness is deposited on the surface of electrode plug by magnetron sputtering which used Pt-W wire as electronic resistance. The exothermicity of Al/CuOx nanothermite multilayer film is so favorable that the ignition ability of electronic initiator is significantly improved. The fully firing-voltage sensitivity of the electronic initiator is 10.8 V. The thickness of Al/CuOx multilayer film has negligible effects on the ignition time and ignition energy, but leads to great impacts on the function time, the maximum length of combustion flame and ignition ability. The electrical ignition experiments have exhibited outstanding ignition ability, since the electronic initiator can easily fire the insensitive ignition composition of boron-potassium nitrate (B-KNO3) tablet in a gap of 20.35 mm. It proves that this novel propose of remolding the tradition electronic ignition devices will distinctly improve the ignition ability and reliability of electronic initiator.