To advance the active safety performance for vehicles, especially in extreme conditions, an active rear steering (ARS) control system is designed in this paper. A driver model is established to simulate the driving behaviour of a human driver who is in charge of the front steering control. In the ARS control system, the sliding mode predictive control (SMPC) approach is applied to the ARS controller design based on a 3 degrees of freedom (DoF) nonlinear vehicle model. In the ARS controller design, four kinds of active safety performances are considered, namely, path-tracking performance, handling performance, lateral stability, and rollover prevention. Furthermore, the priority of the four kinds of active safety performance is defined. According to the control priority, an event-triggered mechanism (ETM) is designed to adjust the SMPC controller of the ARS system to address different driving conditions. Finally, two simulation cases are conducted to evaluate the performance of the proposed ARS system. The results show that the ARS system is in favour of the active safety performance advancement for human drivers. Additionally, the comparative simulation indicates that the SMPC algorithm is superior to the fast terminal sliding mode control (FTSMC) algorithm.