The widespread use of electronics in more avenues of consumer use is increasing. Applications range from medical instrumentation that directly can affect someone's life, down hole sensors for oil and gas, aerospace, aeronautics, and automotive electronics. The increased power density and harsh environment makes the reliability of the packaging a vital part of the reliability of the device. The increased importance of analog devices in these applications, their high voltage and high temperature resilience is resulting in challenges that have not been dealt with before. In particular packaging where insulative properties are vital use polymer resins modified by ceramic fillers. The distinct dielectric properties of the resin and the filler result in charge storage and release of the polarization currents in the composite that have had unpredictable consequences on reliability. The objective of this effort is therefore to investigate a technique that can be used to measure the polarization in filled polymer resins and evaluate reliable molding compounds. A valuable approach to measure polarization in polymers where charge release is tied to the glass transition in the polymer is referred to as thermally stimulated depolarization current (TSDC) technique. In this dissertation a new TSDC measurement system was designed and fabricated. The instrument is an assembly of several components that are automated via a LabVIEW program that gives the user flexibility to test different dielectric compounds at high temperatures and high voltage. The temperature control is enabled through the use of dry air convection heating at a very slow rate enabling controlled heating and cooling. Charge trapping and de-trapping processes were investigated in order to obtain information on insulating polymeric composites and how to optimize it. A number of material properties were investigated. First, polarization due to charges on the filer were investigated using composites containing charged and uncharged particles using quartz and ion exchange montmorillonite silicates in an epoxy matrix. The thermally-activated charge release shows a difference in the composite characteristics and preparation. This difference indicates that the trap levels depend on the de-trapping process and on the chemical nature of the trap site. Using a numerical approach to the release spectra, a model was developed to examine through short time testing, important parameters such as glass transition temperature, residual polarization, depolarization peak, window polarization modeling and activation energy of relaxations. Second the design of mold compounds that could combine manufacturing (temperature of molding), geometric (thickness of packaging material), composition (amount and size of filler) effects was developed using a novel design of experiments approach. The statistical DOE enabled the determination of which causes should be considered when designing a mold compound that has minimal polarization both as singular variables as well as combined variables. Finally, the DOE approach was used to develop a high temperature reliable molding compound through use of combined fillers of thermally conductive and nonconductive fillers having different shapes. Through the systematic approach to developing a technique and designing a mold compound addressing the multiple impacts on reliability of packaging, the dissertation provides an approach to the design, selection, performance and durability of molding compounds.