This article focuses on the fine characterization of steels commonly used in the petrochemical industry damaged by the phenomenon of high temperature hydrogen attack (HTHA). The study was conducted in two steps. To begin with, a damaged 0.5-Mo pearlitic steel from the petroleum refineries, submitted to HTHA for decades, was characterized in detail using multiscale electron microscopy techniques. As part of an upstream study to better understand the onset and the growth of cavities, a brand new SA516 grade 60 low carbon–manganese steel was subsequently exposed to accelerated HTHA conditions through interrupted cycles carried out in autoclaves and then examined. Numerous cavities, plausibly filled with methane, were noticed in both materials. These cavities were mostly located at ferrite–pearlite grain boundaries along carbides and at triple grain boundaries near large carbides. The 0.5-Mo pearlitic steel showed cavities reaching significant sizes, up to 1 µm, but surprisingly no cracks were observed in the depth of the pipe. The major outcome is that 3D focused ion beam–scanning electron microscopy combined with transmission electron microscopy (TEM) analyses unveiled different natures of precipitates as well as in and nearby HTHA cavities for both 0.5-Mo and low carbon–manganese steels. Inclusions, likely AlN, but also Mo- and Cu-rich precipitates were observed in cavities of the industrial steel. These results confirmed a previous study performed on a similar industrial steel that drew a possible correlation between cavities nucleation and the intersection of transgranular inclusion-enriched plane with a grain boundary or carbides in pearlite grains (Flament in Microscopy and Microanalysis 28:1602–1604, 2022).