A variable structure controller with an optimized sliding surface is proposed for slew maneuver of a rigid spacecraft. Rodrigues parameters are chosen to represent the spacecraft attitude. The quadratic type of performance index is used to design the sling surface. For optimization of the sliding surface, a Hamilton- Jacobi-Bellman equation is formulated and it is solved through the numerical algorithm using Galerkin approximation. The solution denotes a nonlinear sliding surface, on which the trajectory of the system satisfies the optimality condition approximately. Simulation result demonstrates that the proposed controller is effectively applied to the slew maneuver of a rigid spacecraft.