Brake time delay, which is a major shortcoming of air brake systems, may lead to precarious situations. In this study, the structure of an air brake system of a tractor–semitrailer was optimized by adding a shuttle valve and a two-position-three-port electromagnetic valve between the control pipeline and the charging pipeline downstream of the trailer control valve. The new electronically controlled structure clearly ensures that the semitrailer brakes faster, as validated by a simulation, bench test, and real-vehicle test. The simulation results reveal considerable improvements in the braking time, braking distance, longitudinal kinetic energy, lateral kinetic energy, and β phase plane. The bench test indicates that in the proposed structure, the average response time of service brake cylinders of the first and third axles of the semitrailer are 0.12 and 0.17 s, respectively. In addition, the real-vehicle test indicated that the service brake cylinders of the first and third axles responded 0.12 and 0.18 s earlier than those in the original system, respectively.