This article proposes a novel adaptive neural optimal control scheme for the uncertain unmanned surface vehicle (USV) system. The proposed adaptive neural optimal control scheme is composed of a neural feedforward controller and a neural optimal feedback controller. The neural feedforward controller is designed by using neural networks (NNs) and the backstepping control design technique to make the unknown nonlinear dynamics of USV system to be stabilized. The neural optimal feedback controller is designed based on adaptive dynamic programming (ADP) theory. It is proved that the formulated adaptive neural optimal control scheme can achieve all signals in USV system are uniformly ultimately bounded (UUB) and the cost function is minimized. The simulation and comparison results demonstrate the effectiveness of the proposed optimal control scheme.