Austenitic steel is a candidate material for supercritical water-cooled reactor (SCWR). This study is to investigate the stress corrosion cracking (SCC) behavior of HR3C under the effect of supercritical water chemistry. A transition phenomenon of the water parameters was monitored during a pseudocritical region by water quality experiments at 650°C and 30 MPa. The stress–strain curves and fracture time of HR3C were obtained by slow strain rate tensile (SSRT) tests in the supercritical water at 620°C and 25 MPa. The concentration of the dissolved oxygen (DO) was , and the strain rate was . The recent results showed that the failure mode was dominated by intergranular brittle fracture. The relations of the oxygen concentration and the fracture time were nonlinear. of oxygen accelerated the cracking, but a longer fracture time was measured when the oxygen concentration was increased to . Chromium depletion occurred in the oxide layer at the tip of cracks. Grain size increased and chain-precipitated phases were observed in the fractured specimens. These characteristics were considered to contribute to the intergranular SCC.