Aiming at the attitude control of the spherical underwater robot, the kinematics and dynamics of the underactuated attitude control adjusting system are analyzed, and its dynamics model is established. By using the differential homeomorphism transformation, the model was divided into two subsystems. Based on the advantages of sliding mode variable structure control, this paper adopts the hierarchical sliding mode variable structure method to design the sliding mode of different variables respectively, and then designs the sliding mode of the whole system. The presented control scheme can solve the coupling problem well. The controller has small overshoot and can well suppress chattering phenomenon. The simulation results show that the designed control law can make the system converge quickly and control the attitude of the underwater spherical robot effectively.