In this paper, a novel iterative Q-learning algorithm, called "policy iteration based deterministic Qlearning algorithm", is developed to solve the optimal control problems for discrete-time deterministic nonlinear systems. The idea is to use an iterative adaptive dynamic programming (ADP) technique to construct the iterative control law which optimizes the iterative Q function. When the optimal Q function is obtained, the optimal control law can be achieved by directly minimizing the optimal Q function, where the mathematical model of the system is not necessary. Convergence property is analyzed to show that the iterative Q function is monotonically non-increasing and converges to the solution of the optimality equation. It is also proven that any of the iterative control laws is a stable control law. Neural networks are employed to implement the policy iteration based deterministic Q-learning algorithm, by approximating the iterative Q function and the iterative control law, respectively. Finally, two simulation examples are presented to illustrate the performance of the developed algorithm.