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Service enterprise workflow simulation is an important approach to analyze service enterprise business processes dynamically. Traditionally, service workflow simulation is based on the discrete event queuing theory, which lacks flexibility and scalability. To address this problem, this paper proposes a service workflow simulation framework based on multi-agent cooperation. Social rationality of software agents is introduced into the proposed framework. Adopting rationality as a decision making strategy facilitates the implementation of flexible scheduling for activity instances. A simulation system prototype is developed and a business case study is conducted to validate the proposed framework.