A surrogate safety measure can be used for preventing hazardous roadway events by evaluating the potential safety risk by using information on the driving environment gathered from vehicles. In this paper, the deceleration-based surrogate safety measure (DSSM) is proposed as a safety indicator for rear-end collision risk evaluation based on the safety conditions and the decision-making process during human driving. The DSSM shows how drivers deal with collision risk differently in acceleration and deceleration phases. The proposed surrogate safety model has been validated for severe deceleration behavior, which is a driver-critical behavior in high-risk situations of collision based on microscopic vehicle trajectory data. The results indicate that there is a strong relationship between the proposed surrogate safety measures and crash potential. The measure could be used for collision warning and collision avoidance systems. It has a merit in that it reflects the characteristics of both vehicle (e.g., mechanical braking capability) and driver (e.g., preference for certain acceleration rates).