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Web service composition is an emerging paradigm for enabling application integration within and across organizational boundaries. Model checking is a promising technique for the verification and validation of software systems. In this paper, we present a model checking framework to specifying and verifying the compositions of Web services workflow based on BPEL4WS (Business Process Execution Language for Web Services). By using annotation layers, a BPEL4WS model can be extended with constraints (properties) information. An underlying BPEL4WS model and one or more constraint annotation layers compose a complete specification of a business process imposed specific constraints. By transforming the annotated BPEL4WS model to an extended TPPN(Timed Predicate Petri-net) model, a business process can be automatically verified and analyzed. The method allows us to add conveniently constraints information to a business process model, and state whether a process satisfies given properties without actual execution based on its specification.