Electrodes based on PEDOT:PSS are gaining increasing importance as conductive electrodes and functional layers in various sensors and biosensors due to their easy processing and biocompatibility. This study investigates PEDOT:PSS/graphene layers deposited via spray coating on flexible PET substrates. The layers are characterized in terms of their morphology, roughness (via AFM and SEM), and electrochemical properties in artificial sweat using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The layers exhibit dominant capacitive behavior at low frequencies, with cut-off frequencies determined for thicker layers at 1 kHz. The equivalent circuit used to fit the EIS data reveals a resistance of about three orders of magnitude higher inside the layer compared to the charge transfer resistance at the solid/liquid interface. The capacitance values determined from the CV curves range from 54.3 to 122.0 mF m-2. After 500 CV cycles in a potential window of 1 V (from -0.3 to 0.7 V), capacitance retention for most layers is around 94%, with minimal surface changes being observed in the layers. The results suggest practical applications for PEDOT:PSS/graphene layers, both for high-frequency impedance measurements related to the functioning of individual organs and systems, such as impedance electrocardiography, impedance plethysmography, and respiratory monitoring, and as capacitive electrodes in the low-frequency range, realized as layered PEDOT:PSS/graphene conductive structures for biosignal recording.