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The purpose of this research is to enhance the analysis of the reliability status for external anticorrosive coatings. With the limitation and insufficiency of the static evaluation method, we study and construct an evaluation method of dynamic reliability for the anticorrosive layer, integrating the trend analysis of the Markov chain and the set pair theory. This method is implemented by the machine learning software of PyCharm community edition, based on Python language. The algorithm utilizes the connection degree in the set pair theory to determine the risk levels of the anticorrosive coating systems. According to the characteristics of the dynamic change of the anticorrosive layer with time, we built the mathematical evaluation model by combining it with the nonaftereffect property of the Markov chain. Therefore, we can make a dynamic and useful analysis for the reliability grade of the anticorrosive coating and assess the effectiveness grade of the changed reliability for the anticorrosive coating after some time. This method can effectively evaluate the reliability level of the anticorrosion coating through the example of big data of detection points. Under national standards, we provide the theoretical basis for pipeline maintenance within detection cycle requirements.