This work introduces two measurement techniques for precision determination of ultra-low conductivity and accurate characterization of dielectric frequency response for the assessments of polymeric materials used in HVDC insulations. To demonstrate the proposed methods, electrical properties of four different low density polyethylene (LDPE) specimens, obtained by different manufacturing processes were characterized. Results obtained from dc conductivity measurements revealed clear separation of the conduction current levels in the studied specimens. Dielectric losses obtained from the frequency response measurements agrees well with the differences observed in the measured conductivities. This study concludes that the different manufacturing processes have a significant impact on materials electric properties and these parameters can be characterized with precision beyond the existing instruments' specification by using the proposed methods.