The microstructures of steels are altered when exposed to high working temperatures for long periods, which results in varied physical and chemical proprieties. This study evaluates the erosive wear behavior of ASTM A106 steel after it is exposed to high temperatures for long durations. Samples of normalized ASTM A106GrB steel were placed in a muffle furnace at 530 and 630 °C for 50, 100, and 200 h. The erosive wear test was conducted at a speed of 20 m/s for 30 min at 450 °C with an incidence angle of 30°. Irregular alumina was used as the erodent material. The surface characterization was performed using scanning electron microscopy to determine the distribution homogeneity, morphological conditions, quantity, and spheroidization degree of the carbides. The erosive wear test results indicated that there was no volume loss after 50 h of heat treatment at 530 °C. The maximum spheroidization degree was 0.71 after 200 h at 630 °C, which decreased the hardness from 220 to 140 HV. Additionally, the volume loss reached 2.52 cm³. Therefore, the use of the ASTM A106GrB steel at working temperatures higher than 530 °C for more than 50 h decreased the mechanical behavior and the wear resistance, thereby decreasing the lifetime of the system.