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Recently discovered polyhedral structures of the value function for finite state-action discounted Markov decision processes (MDP) shed light on understanding the success of reinforcement learning. We investigate the value function polytope in greater detail and characterize the polytope boundary using a hyperplane arrangement. We further show that the value space is a union of finitely many cells of the same hyperplane arrangement and relate it to the polytope of the classical linear programming formulation for MDPs. Inspired by these geometric properties, we propose a new algorithm, Geometric Policy Iteration (GPI), to solve discounted MDPs. GPI updates the policy of a single state by switching to an action that is mapped to the boundary of the value function polytope, followed by an immediate update of the value function. This new update rule aims at a faster value improvement without compromising computational efficiency. Moreover, our algorithm allows asynchronous updates of state values which is more flexible and advantageous compared to traditional policy iteration when the state set is large. We prove that the complexity of GPI achieves the best known bound $\mathcal{O}\left(\frac{|\mathcal{A}|}{1 - γ}\log \frac{1}{1-γ}\right)$ of policy iteration and empirically demonstrate the strength of GPI on MDPs of various sizes.