The intelligent of power systems has led to an ever-increasing demand for communication in substation networks, and traditional communication methods are facing challenges. This paper applies Radio over Fiber (RoF) technology to integrate the strengths of optical fiber and wireless communication, thus supplying a solution for the communication of substation networks. Firstly, the system structure consisting of user terminals, optical fiber links, base stations, and central stations is designed, and the functions of key devices such as hybrid couplers are expounded. Then, the principle of the wavelength reuse full duplex RoF system is analyzed. Once the signal has been processed at the central station, it is conveyed to the base station via the optical fiber. Gratings are used to achieve filtering, demodulation, and uplink carrier reuse. By relying on the system that combines wavelength reuse and wavelength division multiplexing, the principle and application of wavelength division multiplexing are validated. The simulation results demonstrate that this system has advantages such as low loss and large bandwidth in substation network communication. Its feasibility and superiority provide corresponding technical support for the intelligent of substation networks.