Aluminum electrolytic capacitors with polymer electrolytes were developed to obtain lower equivalent series resistance (ESR) than that is achievable with liquid electrolytes. Replacement of the liquid electrolyte with a solid conductive polymer also overcomes the propensity of the liquid to evaporate over time, which leads to a reduction in capacitance and an increase in ESR values. However, capacitor manufacturers acknowledge that humidity can degrade the polymer, thereby having an adverse effect on the reliability of polymer aluminum (PA) capacitors. In the current study, surface mount and thru-hole PA capacitors from two different manufacturers were subjected to highly accelerated stress testing (110 °C, 85% RH) and elevated temperature–humidity (85 °C, 85% RH) conditions for rapid assessment. The polymer electrolyte in the capacitors was poly(3,4-ethylenedioxythiophene). Failure analysis was performed to determine the observed failure modes and the underlying failure mechanisms. The dominant failure modes observed were an increase in leakage current and an increase in ESR.