Protecting metal structures through organic coatings is vital to maintaining the integrity of metallic structures, particularly in the marine transportation industry. In response to the economic significance of marine transportation, there is a continuous research drive towards developing high-performance coatings that offer robust resistance to harsh marine environments. Achieving this goal necessitates employing advanced characterization methods, capable of swiftly and reliably assessing the protective performance of marine coatings. This study aimed to evaluate the feasibility of using an accelerated electrochemical technique (alternating current-direct current-alternating current (AC-DC-AC)) to simulate the degradation of marine primers. A comparative analysis of the AC-DC-AC technique and salt spray test was conducted to evaluate the delamination behavior of neat epoxy (NE), aluminum-pigmented epoxy (AE), and graphene-containing epoxy (GE) coatings. Electrochemical impedance spectroscopy (EIS) was used to monitor the degradation response of the protective properties of the coatings during the exposure to salt spray and the accelerated electrochemical test. The coatings subjected to the accelerated technique showed a similar degradation trend to those exposed to the salt-spray test, validating its reliability in assessing the delamination behavior of barrier coatings. However, the degradation rate was faster in the accelerated test. The graphene-containing coating provided a superior barrier performance compared to the aluminum-pigmented coating.