The class of vehicles that can move both in the air and underwater has been of great interest for decades. A novel water-air unmanned vehicle with double quadrotor structure is designed in this study. The air power mechanism works when the vehicle flies in the air, whereas the water power mechanism works when it moves underwater. The water entry process of water-air unmanned vehicle requires accurate attitude and height control, or the vehicle may bounce off or overturn. However, a force resisting its descent known as in-ground effect will affect its stability. The in-ground effect formula of the water entry process is derived by experiments, and the water entry dynamic model is improved at the same time. An active disturbance rejection controller (ADRC) is designed for the control of water entry attitude and height. Experimental results obtained from the comparison of the ADRC and a proportional-integral-derivative (PID) controller show that the ADRC designed in this study is more robust than the PID controller for the internal coupling and external disturbance on the vehicle. Moreover, the ADRC can meet the requirements of rapid attitude adjustment and accurate height control.