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WS-BPEL language has become the industrial standard to design and orchestrate modular applications, formalizing service compositions and business relationships among providers and consumers. Once service level agreements (SLAs) among the parties are established, effective tools for evaluating appropriate measurements have to be developed to meet the requirements. However, the design of quality of service (QoS)-guaranteed composed Web services (WSes) still requires several efforts. This work aims at proposing a complete method to study the QoS of a composed WS at design time, i.e., when the process is specified by using WS-BPEL. Starting from the nonfunctional properties of the WS to compose, we propose a technique to derive non-Markovian stochastic Petri net (NMSPN) models from WS-BPEL processes, with the final goal of evaluating parameters such as the service time distribution and the service reliability. To demonstrate the effectiveness of the proposed method and to validate the obtained model, a nontrivial example implementing a travel agency flight reservation process, exposed as a synchronous composed WS, is investigated.