In this study, LDPE samples were prepared by melt blending with different cooling processes, which were natural air cooling, rapid air cooling, water cooling and oil cooling, respectively. According to polarization microscope (PLM) and differential scanning calorimeter (DSC) tests of these four low-density polyethylene (LDPE) samples, the effect of different cooling processes on polythene crystalline morphology could be studied. According to conductivity, dielectric frequency spectra and space charge tests, the effect of crystalline morphology on dielectric macroscopic properties could be explored. The microstructure characteristic results indicated the cooling medium significantly affected polythene crystalline morphology. When the samples were produced with natural air cooling, the crystalline grain size was large. On the other hand, after rapid air cooling, water cooling and oil cooling processes, the samples’ crystalline grain dispersed uniformly, and the grain sizes were lower. The space charge testing results indicate the samples produced with water cooling and oil cooling processes restrained the electrode injection in the process of pressurization. During short-circuits, the rates of charge release of these two samples were fast, and the remaining space charges were fewer. The conductivity and dielectric frequency spectra testing results indicated the conductivities of samples produced with water cooling and oil cooling processes were both less than those of samples produced with a natural air cooling process. Besides, with increasing experimental frequency, the relative dielectric constants of all testing samples decreased. Among them, the relative dielectric constant of the LDPE sample with the natural air cooling process was the largest. However, the crystalline structures of samples produced with rapid air cooling and water cooling processes were close, which restrained the movement of polymer macromolecule chains. Thus, the dielectric constants were lower. Additionally, because of the influence of relaxation polarization and dipole polarization, the dielectric losses of LDPE with water cooling and oil cooling processes increased to varying degrees.