Effects of crystallographic quality of grain boundaries on mechanical and electrical properties were investigated experimentally. A novel method using two parameters of image quality (IQ) and confidence index (CI) values based on electron back-scattering diffraction (EBSD) analysis was proposed in order to evaluate crystallographic quality of grain boundaries. IQ value was defined as an index to evaluate crystallinity in region irradiated with electron beam. CI value determined existence of grain boundaries in the region. It was found that brittle intergranular fatigue fracture occurred in the film without annealing and the film annealed at 200 °C because network of grain boundaries with low crystallinity remained in these films. On the other hand, the film annealed at 400 °C caused only ductile transgranular fatigue fracture because grain boundaries with low crystallinity almost disappeared. From results of measurement of electrical properties, electrical resistivity of copper interconnection annealed at 400 °C with high crystallinity (2.09 × 10−8 Ωm) was low and electron migration (EM) resistance was high compared with an copper interconnection without annealing with low crystallinity (3.33 × 10−8 Ωm). It was clarified that the interconnection with high crystallinity had superior electrical properties. Thus, it was clarified that the crystallographic quality of grain boundaries has a strong correlation of mechanical and electrical reliability.