The adaptive cruise control (ACC) problem can be transformed to an optimal tracking control problem for complex nonlinear systems. In this paper, a novel highly efficient model-free adaptive dynamic programming (ADP) approach with experience replay technology is proposed to design the ACC controller. Experience replay increases the data efficiency by recording the available driving data and repeatedly presenting them to the learning procedure of the acceleration controller in the ACC system. The learning framework that combines ADP with experience replay is described in detail. The distinguishing feature of the algorithm is that when estimating parameters of the critic network and the actor network with gradient rules, the gradients of historical data and current data are used to update parameters concurrently. It is proved with Lyapunov theory that the weight estimation errors of the actor network and the critic network are uniformly ultimately bounded under the novel weight update rules. The learning performance of the ACC controller implemented by this ADP algorithm is clearly demonstrated that experience replay can increase data efficiency significantly, and the approximate optimality and adaptability of the learned control policy are tested with typical driving scenarios.