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B2B E-Business is becoming one of the most popular electronic business ways. Because of lacking a unified standard and solution of basic architecture and interface, traditional B2B E-Business system has many shortcomings, such as poor reusability and poor extensibility. In order to solve the problems, a B2B E-Business system model based on Web Service is proposed and analyzed. The model can build relatively independent Web Service on Intranet and Internet by constructing core application program. It is easy to develop, integrate and maintain B2B E-Business system with the model. The paper applies the model to B2B E-Business System of Bookshop, which includes the management subsystem of order, book information, bookshop information, bill information, and customer relations.