The pressure-wave propagation (PWP) method allows for the nondestructive measurement of charge distributions in dielectric materials. This method has been used to study the electrical properties of electrode/polyethylene/electrode structures such as those involved in high-voltage cables. The influence of the composition of the insulating resin itself and that of the electrodes are analyzed in polyethylene samples. According to the chosen combination, charge transfer at the interfaces, migration of ionizable impurities, or a strong decrease of both is observed. This application of the PWP method is of particular interest, since it allows for a suitable choice of the materials and structures involved in insulator/conductor interfaces. >