A Gauss pseudospectral method is proposed in this study to solve the optimal trajectory-planning problem for satellite rapid large-angle maneuvers. In order to meet the requirement of rapid maneuver capability of agile small satellites, Single Gimbal Control Moment Gyros (SGCMGs) are adopted as the actuators for the attitude control systems (ACS). Because the singularity problem always exists for SGCMGs during the large-angle maneuvering of the satellites, a trajectory optimization method for the gimbal rates is developed based on the Gauss pseudospectral method. This method satisfies the control requirement of satellite rapid maneuvers and evades the singularity problem of SGCMGs. The method treats the large-angle maneuver problem as an optimization problem, which meets the boundary condition and a series of the physical constraints including the gimbal angle constraint, the gimbal rates constraint, the singularity index constraint, and some other performance criteria. This optimization problem is discretized as a nonlinear programming problem by the Gauss pseudospectral method. The optimal nonsingularity gimbal angle trajectory is obtained by the sequence of quadratic programming (SQP). This approach avoids the difficulties in solving the boundary value problem. The simulations reveal that the Gauss pseudospectral method effectively plans an optimal trajectory and satisfies all the constraints within a short time.