To solve precise guidance and maneuver penetration problems for hypersonic vehicle in dive phase, the optimal guidance method with maneuver was proposed. Considering that the traditional guidance law based on zero-LOS angle rate can debase penetrative ability, it designed reference motion for the rate in diving-plane and turning-plane. Besides, in order to enhance penetrative ability farther and realize precise guidance, it took advantage of optimal control with the optimal index of maximum terminal velocity to track the LOS angle rate, and pseudo control variable was introduced to simplify the resolution of optimal control problem. Finally, it analyzed the guidance capability and stability of this method. The results of CAV-H vehicle test show that the algorithm can realize maneuvering flight, and can satisfy terminal impact point and falling angle constraints. Therefore, the method can offer reference for high precision guidance and maneuver penetration for hypersonic vehicle in dive phase.