Advanced electrochemical techniques such as electrochemical impedance spectroscopy (EIS), electrochemical noise method (ENM) and coulometry as tools to study and extract information about the coating system is the focus of this thesis. This thesis explored three areas of research. In all the three research areas, advanced electrochemical techniques were used to extract information and understand the coating system. The first area was to use EIS and coulometric technique for extracting information using AC-DC-AC method. It was examined whether the total charge passing through the coating during the DC polarization step of AC-DC-AC determines coating failure. An almost constant total amount of charge transfer was required by the coating before it failed and was independent of the applied DC polarization. The second area focused in this thesis was to investigate if embedded sensors in coatings are sensitive enough to monitor changes in environmental conditions and to locate defects in coatings by electrochemical means. Influence of topcoat on embedded sensor performance was also studied. It was observed that the embedded sensors can distinguish varying environmental conditions and locate defects in coatings. Topcoat could influence measurements made using embedded sensors and the choice of topcoat could be very important in the successful use of embedded sensors. The third area of research of this thesis work was to examine systematically polymer-structure coating property relationships using electrochemical impedance spectroscopy. It was observed that the polymer modifications could alter the electrochemical properties of the coating films. Moreover, it was also observed that by cyclic wet-dry capacitance measurement using aqueous electrolyte and ionic liquid, ranking of the stability of organic polymer films could be performed.