We consider the optimal control of feedback linearizable dynamical systems subject to mixed state and control constraints. In general, a linearizing feedback control does not minimize the cost function. Such problems arise frequently in astronautical applications where stringent performance requirements demand optimality over feedback linearizing controls. In this paper, we consider a pseudospectral (PS) method to compute optimal controls. We prove that a sequence of solutions to the PS-discretized constrained problem converges to the optimal solution of the continuous-time optimal control problem under mild and numerically verifiable conditions. The spectral coefficients of the state trajectories provide a practical method to verify the convergence of the computed solution. The proposed ideas are illustrated by several numerical examples.