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Recently, Web Service technology has found its application in workflow management for supporting loosely coupled E-business processes. However, current Web services languages do not permit to describe distributed E-business services by lack of expressive power and formal semantics. This paper presents a novel method for modeling distributed E-business service composition with pi-calculus technology. Firstly, the syntactic structure of WS-BPEL is analyzed, and an approach to modeling inter-organizational e-business processes with pi-calculus is given. Then, based on the execution semantics of the pi-calculus, the composite behavior of distributed e-business system are defined precisely. Finally, a case study is carried and the effective of composition model is verified.