The paper presents results obtained from the destructive laboratory investigation conducted on materials from pressure vessels after long-term operation in the refinery industry. Tested materials contained structural defects, which arose from improper heat treatment during steel plate manufacturing. Detailed metallographic and chemical composition tests and static tensile tests were conducted. Next, complex tensile tests were conducted with simultaneous acoustic emission (AE) monitoring while observing microstructural changes by light microscopy. From the laboratory tests, the correlations between the AE signal parameters and material microstructural damage during the tensile tests were developed. The results will be used as a basis of new algorithms for the structural condition assessment of in-service pressure equipment.