Web service orchestration languages describe executable business processes composed of Web services. A business process can fail for many reasons, such as faulty Web services or mismatching messages. It is important to find out which Web services are responsible for a failed business process because we could penalize these Web services and exclude them from the business process in the future. In this paper, we propose a model-based approach to diagnose orchestrated Web service process. We convert the Web service orchestration language, BPEL4WS, into synchronized automata, so that we have a formal description of the topology and variable dependency of the business process. After an exception is thrown, the diagnoser can calculate the business process execution trajectory based on the formal model and the observed evolution of the business process. The faulty Web services are deduced from the variable dependency on the execution trajectory. We demonstrate our diagnosis technique with an example.