Chloride ion diffusion at the corner of rectangular-shaped concrete structures is presented. At the corner of rectangular-shaped concrete, chloride ion diffusion is in two-dimensional process. Chloride ions accumulate from two orthogonal directions, so that corrosion-free life of concrete structures is significantly reduced. A numerical procedure based on finite element method is used to solve the two-dimensional diffusion process. Orthotropic property of diffusion coefficient of concrete is considered and chloride ion profile obtained from numerical analysis is used to produce transformed diffusion coefficient. Comparisons of experimental data are also carried out to show the reliability of proposed numerical analysis. As a result of two-dimensional chloride diffusion, corrosion-free life of concrete structure for railway is estimated using probability of corrosion initiation. In addition, monographs that produces transformed diffusion coefficient and corrosion-free life of concrete structure are made for maintenance purpose.