Aiming at problems existing in current substation training systems, such as weak to fault simulation, the lack of the sensed presence and simple inspection way, the immersive substation accidents simulation system is developed. The simulation object is a 110 kV substation. And the perfect interactive functions offered by Unity3D and the powerful hardware support of HTC vive are used in this system. Firstly, the models of substation’s primary equipment are established by 3DMAX software, then the models are imported into Unity3D software, the immersion interactive scenario is set by the SteamVR plug-in, and the faults information and equipment information are deposited into the MySQL database. In this way, the student assessment module is developed. This system realizes the functions of immersion training in substation and student assessment of failure. In the process of system development, the hardware platform of HTC vive is used to bring the immersion for student’s training. It inspires the student’s passion and improves the training efficiency. And the design of the assessment module completes the evaluation function of the system, and provides the evaluation evidences for the student’s study. This work is supported by National Natural Science Foundation of China (No. U1404612).