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In this paper, a method of automatic composition based on pi-calculus for semantic Web service has been presented to improve the automation composition of semantic Web service. First, the formal model of the semantic Web service composition based on pi-calculus is represented, and eight kinds of basic Web service composition patterns in service model of OWL-S are provided. These patterns can be utilized to construct Web service on demand. Then the matching between existing web services and sub-services are verified by the formalization and verification of pi-calculus, and the Web service composition is realized finally.