In this article, we develop an aqueous electrode technique that can adapt to complex sample geometries while maintaining perfect contact between the electrodes and the measured sample. In contrast to surface deposited electrodes, the aqueous electrode technique measures the ionic conduction of the polymer sample instead of the inherent dielectric properties of the polymer. Polymer ionic conduction is often related to the polymer thermodynamic state, which itself is closely linked to many other polymer properties. As such, the aqueous electrode method provides an approach to conduct in situ monitoring of polymer samples subjected to degradation; changes in the impedance provide an indication of polymer sample degradation. This article presents the aqueous electrode setup and discusses experimental results obtained using it. Changes in the impedance response of PVC and polyimide films due to moisture absorption, ionic conduction, pinholes, chemical degradation, and temperature are presented. POLYM. ENG. SCI., 49:441-453, 2009. (c) 2008 Society of Plastics Engineers