Hydrogen/air rotating detonation turbine engine is expected to become a new generation of aerospace power plant because of its compact structure, high cycle thermal efficiency, and superior thrust performance. It can also reduce fuel consumption, save energy, and reduce carbon emissions. However, the highly unsteady oscillation characteristics of the outlet flow of the rotating detonation combustor make it difficult to integrate the supersonic turbine with the rotating detonation combustor. In this paper, the supersonic turbine guide vanes are designed by the method of characteristics and Bessel parameterization and are integrated with three-dimensional hydrogen/air rotating detonation combustors for numerical studies. The effects of aligned mode and misaligned mode on the coupling of supersonic turbine guide vanes and rotating detonation combustor are discussed carefully. The results show that the supersonic turbine guide vanes can make the rotating detonation wave change from a single-wave mode to a double-wave alternating strength and weak propagation mode. It can effectively suppress the oscillation of the combustion chamber outlet airflow. In the aligned mode, the peak pressure at the outlet of the supersonic turbine is about 70% lower than that at the cascade inlet, the pressure oscillation amplitude is reduced by 93.33%, and the temperature amplitude is reduced by 23.81%; the average total pressure loss coefficient of the cascade is 11.63%. In the misaligned mode, compared with the cascade inlet, the peak value of the pressure signal at the cascade outlet decreases by about 50%, while the pressure oscillation amplitude decreases by about 33.33%, and the temperature oscillation amplitude decreases by 11.11%; the average total pressure loss coefficient of the cascade is 4.83%. The supersonic turbine guide vanes have a better suppression effect on the oscillation signal in the aligned mode, but the relative total pressure loss is relatively large. This is because that the oblique shock wave, channel shock wave, and supersonic turbine guide vanes interact to generate more complex wave system and secondary flow in the aligned mode. These features provide important reference information for the coupling of supersonic turbines and rotating detonation combustors.