Abstract Mechanical property of coarse grained and nano/ultrafine grained alloy 690 and their corrosion resistance after immersion in high temperature borate buffer solution were investigated. The grain refinement significantly enhances the tensile strength of the alloy 690. In addition, the grain refinement facilitates the formation of the deformation twin which improves the ductility of the alloy 690. It has been found that the grain refinement promotes to form more Cr2O3 on the surface of the alloy 690 in high temperature borate buffer solution. At the same time, the grain refinement inhibits the formation of spinel type oxides. More hematite type oxides formed on nano/ultrafine grained alloy 690 improves its corrosion resistance in borate buffer solution. The hematite type oxides have a lower concentration of point defect than that of the spinel type oxides, which results in an excellent corrosion resistance of nano/ultrafine grained alloy 690. These results are supported by the Mott-Schottky analysis and the point defect model.