The HR3C is a new steel for pressure components used in the construction of boilers with supercritical working parameters. In the HR3C steel, due to adding Nb and N, the compounds such as MX, CrNbN and M23C6 precipitate during service at elevated temperature, resulting in changes in mechanical properties. This paper presents the results of microstructure investigations after ageing at 650, 700 and 750 °C for 5,000 h. The microstructure investigations were carried out using scanning and transmission electron microscopy. The qualitative and quantitative identification of the existing precipitates was carried out using X-ray analysis of phase composition. The effect elevated temperature on microstructure and mechanical properties of the examined steel was described.