The purpose of this study is to evaluate the proliferation resistance characteristics for different fuel cycle arrangements in the context of a global nuclear energy system using a Markov approach, which is capable of modeling complex systems and providing probabilistic measures. A technique that groups a set of reactors similar to each other and yet captures major fuel cycle features for proliferation study is proposed as an enhancement to the Markov approach to reduce the modeling complexity. In evaluating impacts on proliferation, both the amounts of total materials around the world and the amounts of materials that are used by the host state are considered. Proliferation concerns are represented based on the proliferation resistance measures of fuel cycles. In addition to representing proliferation impact in terms of proliferation success probability, a measure of proliferation risk is also introduced by using a product of the proliferation success probability and the material type index that represents the consequence of the proliferation. Sensitivity analyses are performed by varying the scale of the nuclear energy system owned and operated by a host state.