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Grain boundary engineering (GBE) via low strain tension and annealing was used to enhance the resistance to stress corrosion cracking of a 304 stainless steel. Electron backscattered diffraction (EBSD) analysis exhibited that the GBE steel had a higher fraction of low-∑ coincidence site lattice (CSL) boundaries, larger grain-clusters, longer twin boundary chains, and fewer paths of connected non-twin boundaries with a more zigzag shape. Slow strain rate tests in high-temperature water showed that the GBE steel performed better plasticity, higher tensile strength, and similar yield strength compared to conventional steel. The low fraction of random boundaries in GBE steel resulted in a lower frequency of intergranular crack initiation, and the zigzag paths of non-twin boundaries made the intergranular crack propagation more difficult.