In this article, a novel reinforcement learning-based optimal tracking control (RLOTC) scheme is established for an unmanned surface vehicle (USV) in the presence of complex unknowns, including dead-zone input nonlinearities, system dynamics, and disturbances. To be specific, dead-zone nonlinearities are decoupled to be input-dependent sloped controls and unknown biases that are encapsulated into lumped unknowns within tracking error dynamics. Neural network (NN) approximators are further deployed to adaptively identify complex unknowns and facilitate a Hamilton-Jacobi-Bellman (HJB) equation that formulates optimal tracking. In order to derive a practically optimal solution, an actor-critic reinforcement learning framework is built by employing adaptive NN identifiers to recursively approximate the total optimal policy and cost function. Eventually, theoretical analysis shows that the entire RLOTC scheme can render tracking errors that converge to an arbitrarily small neighborhood of the origin, subject to optimal cost. Simulation results and comprehensive comparisons on a prototype USV demonstrate remarkable effectiveness and superiority.