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Organic coatings are widely used to control the corrosion of steel structure. The anticorrosive property of these coatings depends on their barrier properties, making a separation between the corrosive medium and the substrate. But unavoidable completely small pores, cracks and other defects in organic coatings may cause ions, water, gases, and other corrosive species penetrate and distribute in the coatings, causing accumulation and swelling of coatings, so leading to the degradation of coatings. In addition, water affects the permeation of oxygen and other corrosive medium, consequently the presence of such substances at coating-metal interface promotes corrosion of metal substrate. So the absorbability of the coatings to water may be one of the most important factors in undercoating corrosion. In recent years, electrochemical impedance spectroscopy (EIS) has been established and frequently used as a non-destructive testing method for assessing the performance of organic coatings, especially for the determination of the water content in organic coatings, since the capacitance of the coatings is sensitive to the penetration of water. So from EIS it can extract a wealth of information on the electrochemical corrosion of coated steels, especially, it can be utilized to assess organic coatings used under particular surroundings. The principle, methods and application of EIS on evaluating life-span and analyzing failure mechanism of organic coatings are also introduced briefly. Combining other analysis techniques such as XRD, SEM and FTIR with electrochemical technique, it will blaze a way in studying degradation mechanism of organic coatings and estimating their lifetime.