The electrical properties of polyethylene are changed by the superstructure. Such crystalline polymer as polyethylene or polypropylene changes crystallinity and products spherulite or trans-crystal when it is cooled slowly. In this study, after thermal treatment of LDPE at 100[${circ}C$], in silicone oil for an hour, we made specimens in order of slow cooling, water cooling, quenching according to cooling speed. Also, to study the influence of electrical properties due to the superstructure change, we analyzed physical properties and performed dielectric breakdown experiments using DC and impulse voltage Moreover we measured space charges in bulk using Laser Induced Pressure Pulse(LIPP) method. Trap level of specimen is 0.064[eV] at the low temperature region 0.31[eV] at the high temperature region in DC dielectric strength, 0.03[eV] at the low temperature region 0.0925[eV] at the high temperature region in impulse dielectric strength. As its result shows that the quantity of charges induced from the electrode surface increases with applied voltage time, and the distribution of space charges in samples increases the quantity of charges in proportion to applied voltage.