The microstructure evolution and stress corrosion cracking (SCC) behaviors of ultrafine-grained (UFG) Cu-Cr-Zr alloys processed by equal-channel angular pressing (ECAP) and coarse-grain (CG) Cu-Cr-Zr alloys within NaNO2 solution were systematically investigated in the current study. After deformation by eight ECAP passes, the grain size was refined to ~200 nm. The slow strain rate tensile (SSRT) tests showed that the ultimate tensile strength (UTS) of CG samples in solution was slightly lower than that in the air, and the elongation was decreased from 57.3% to 52.6%. In contrast, both the UTS and elongation of UFG samples in air and solution were almost identical. In NaNO2 solution, the CG fracture surface showed an obvious dissolution, microvoids, and minor cracks, while the surface of the UFG fracture was relatively smooth. The resistance of UFG samples to SCC could be significantly enhanced compared with CG samples. The grain boundary volume fraction of UFG alloy was dramatically increased, which reduced the formation of pitting corrosion. In addition, the uniform distribution of Cr particles also improved the corrosion resistance of UFG alloys.