Electrochemical monitoring of electrical and structural changes of both PPy and PPy–PEG films electrochemical deposited, in order to highlight if the structural stability offered by PEG has an influence on electrical properties and stability in aqueous solution over immersion time was investigated. Electrochemical analysis suggests that PPy–PEG film inserts cations easier than PPy film for a short immersion time probably due to ability of PEG to form complexes with metal cations. The FTIR spectra showed that the PEG incorporation decreases the rate of PPy overoxidation probably by restraining the electron release and by rendering O2 inaccessible to PPy. Mott–Schottky analysis based on capacitance measurement reveal p-type conductance for both films. The in situ AFM analysis sustains electrochemical behaviour and has permitted elaboration of a model of PPy and PPy–PEG films behaviour during immersion in testing solution.