It is recognized that the application of constrained optimal control for wave energy converters (WECs), represented by model predictive control (MPC), is hindered by its computation burden resulting from online optimization, especially when the model contains nonlinearities. In this article, a novel control solution based on approximate dynamic programming (ADP) is proposed, in which an explicit controller is solved by model sampling and neural network training. In this way, the major computation load is moved offline to enable fast online execution, and the need for wave prediction is eliminated. The effectiveness of ADP is verified by a simulation case study based on a nonlinear WEC system. Using nonlinear MPC as the performance benchmark, over 90% energy efficiency is achieved by ADP under various sea states with constraint satisfaction and dramatically faster computation. The ADP controller is further experimentally validated on a newly constructed WEC prototype through wave tank testing, where successful implementation and satisfactory performance are demonstrated.