An influence of the addition of copper (0.5, 1.0 and 1.5 mass% Cu) on the microstructure and mechanical properties of high purity iron (99.998 mass%) was characterized. The microstructure and microhardness of high-purity iron based samples, which were rolled at room temperature and subsequently annealed, were investigated in this work. The microstructure of the samples has been observed by electron back scattering diffraction (EBSD) and the mechanical properties have been studied by using micro-Vickers hardness test. The results of microstructural observation showed that deformation band was formed in high purity iron by rolling at room temperature, and it was recovered by annealing up to about 900 K. The microhardness results showed that the softening of high-purity iron occurred by annealing up to about 900 K, while the hardness of iron added with about 0.5-1.5 mass% copper was kept over 100 Hv and at the early time of annealing reached a maximum. The hardness of iron added with a small amount of copper may be attributed to precipitation hardening as well as solution hardening. The orientation of crystal in recrystallized grain was almost same as that of deformed grain.