In this paper, the mechanical properties of various zones of the welded joints of a heat-resistant steel 15Kh1M1F in different states (in the initial state, after an operation on the main steam piping of a thermal power plant (TPP) for 23 years) were determined, and the fracture surfaces were analyzed using scanning electron microscopy (SEM) images. The effect of hydrogen electrolytic charging on mechanical behavior and fracture mechanism was also studied. The long-term operation of welds resulted in a higher degradation degree of the weld metal compared to the base one, indicated by the deterioration of mechanical properties: decrease in hardness, strength characteristics, and reduction in area, which was accompanied by an atypical increase in elongation at fracture. All studied zones of the operated welded joints were characterized by higher hydrogen content, 2.5–3 times higher than that in the initial state. Additional hydrogen charging of the weld joint metal led to a decrease in the strength and ductility characteristics, more significantly for the operated weld compared with the non-operated one. This justified the possibility of using short-term tests of hydrogenated WM in the air to assess the degree of its damage during operation on a steam piping.