The use of conductive polymers in aluminium electrolytic capacitors prevents leakage and enlarges the temperature use range when compared with their liquid counterparts. PEDOT:PSS is an outstanding candidate due to its tunable properties, i.e., electronic conductivity (10−5 to 103 S/cm), and its high thermal stability. As a result of their synthesis, PEDOT:PSS dispersions are characterized by a low pH value, which can influence pH sensitive materials such as aluminium. However, no work to date has studied the interaction between PEDOT:PSS dispersions and aluminium oxide substrates. In this work, the interface and interaction between PEDOT:PSS and an aluminium electrode were studied for the first time via odd random phase electrochemical impedance spectroscopy and analysed post mortem by SEM and AFM characterization. PEDOT:PSS dispersions at different pH values (1.9, 4.9, 5.8) were applied in a layered manner onto a non-etched aluminium substrate with a grown oxide layer on top, which provided a model system for the analysis of the interface. The analysis showed that the acidic PEDOT:PSS dispersions attacked the aluminium substrate, forming pores on the surface, but had a positive impact on the capacitance of the aluminium oxide/PEDOT:PSS systems. On the other hand, neutral dispersions did not affect the aluminium electrode, but showed poor layer formation properties, and the electrochemical analysis displayed a dispersion of results ranging from capacitive to resistive behaviour.