Through the variable substitution and separated variable methods, this study develops a two‐dimensional (2‐D) axisymmetric diffusion analytical solution for organic pollutants in a circular‐shaped cutoff wall (CCW) system for the first time, which can more precisely and reasonably simulate the diffusion behaviors in “circular‐shaped” vertical barriers. Then, the proposed analytical solution's reasonableness is verified by comparing it with an existing analytical solution and a corresponding finite‐difference solution. Meanwhile, the comparison suggests that this solution will degrade to a 2‐D diffusion analytical solution when the pollution source radius is large enough. Furthermore, the presented analytical solution can also be simplified to a one‐dimensional axisymmetric diffusion analytical solution, or to the axisymmetric diffusion analytical solutions in a single‐layered medium. These exact analytical solutions can not only be applied to study axisymmetric diffusion behaviors under specific scenarios, but also be used to validate other complex numerical models. Last, a case study is conducted to investigate the impacts of pollution source concentration distribution, CCW horizontal thickness, and defined equivalent diffusion coefficient on the barrier performance. Overall, the proposed analytical solutions and obtained diffusion laws in this study can provide guidance for the service effect assessment and the engineering design of cutoff walls.