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In order to realize a high quality and good performance service composition, we propose new QoS driven dynamic selection of composite Web services, which takes account of both the QoS properties and interface parameter matching degree. When doing the selection, we are aware that the task is more or less a multistage decision making process. Motivated by transiently chaotic neural network high parallel performance and powerful computation ability, a new structured transiently chaotic neural network algorithm is proposed. In order to make this algorithm more adaptable for the multistage decision making problem, we propose a new structured neural network to express the composed service instead of using traditional neural networks, which minimizes the neurons involved and shows higher performance. Finally, through experimentation one can find that the method proposed in this paper is more practical and effective than others.