This paper presents a switching PD-based sliding mode control (PD-SMC) method for the 6-degree-of-freedom (DOF) hovering motion of the underwater robot with tilting thrusters. Four thrusters of robot can be tilted simultaneously in the horizontal and vertical directions, and the 6-DOF motion is achieved by switching between two thruster configurations. Therefore, the tilting speed of thruster becomes the most essential parameter to determine the stability of hovering motion. Even though the previous PD control ensures stable hovering motion within a certain ranges of tilting speed, a PD-SMC is suggested in this paper by combining PD control with sliding mode control in order to achieve acceptable hovering performance even at the much lower tilting speeds. Also, the sign function in the sliding mode control is replaced by a sigmoid function to reduce undesired chattering. Simulations show that while PD control is effective only for tilting duration of 600 ms, the PD-based sliding mode control can guarantee the stable hovering motion of underwater robot even for the tilting duration of up to 1500 ms. Extensive experimental results confirm the hovering performance of the proposed PD-SMC method is much superior to that of PD method for much larger tilting durations.