Aiming at the penetration problem of high-speed vehicles against a modified proportional guidance interceptor, a three-dimensional mathematical model of attack–defense confrontation between the high-speed vehicle and the interceptor is established in this paper. The modified proportional navigation guidance law of the interceptor is included in the model, and control constraints, pitch angle velocity constraints, and dynamic delay are introduced. Then, the performance index of the optimal penetration of high-speed vehicles is established. Under the condition of considering the 180-degree BTT control, the analytical solutions of the optimal speed roll angle and the optimal overload of high-speed vehicles are obtained according to symmetric Hamilton principle. The simulation results show that the overload switching times of high-speed vehicles to achieve optimal penetration are N − 1, where N is the modified proportional guidance coefficient of the interceptor. When the maximum speed roll angle velocity is [60, 90] degrees per second, the penetration effect of high-speed vehicles is good. Finally, the optimal penetration guidance law proposed in this paper can achieve a miss distance of more than 5 m when the overload capacity ratio is 0.33.