The performance of the model-based controller is always affected by the uncertainty and nonlinearity of the model parameters in the vehicle path tracking process. To address this issue, a novel path tracking controller based on model-free adaptive dynamic programming (ADP) is proposed for autonomous vehicles in this paper. To be specific, the proposed controller obtains information from the online state and front-wheel angle input data which are repeatedly used to calculate the controller gain iteratively. So, this controller features not requiring accurate knowledge of vehicle model parameters for controller development. Meanwhile, the path tracking performance of the autonomous vehicle will be inevitably disturbed by unknown nonlinear external disturbance. To approximate this disturbance, the learning characteristics of Radial Basis Function Neural Network (RBFNN) are applied to generate compensation for the front-wheel angle. Afterward, the weight updating law of RBFNN is derived by Lyapunov function to ensure the stability and convergence of the whole system. Finally, Hardware in the loop (HIL) test results demonstrate that the proposed ADP-RBF controller can improve the comprehensive performance of the vehicle path tracking control system and achieve the balance between path tracking accuracy and minimum sideslip angle.