With the adoption of service-oriented manufacturing modes, more and more manufacturing services are released over manufacturing service platforms. As it is known, the problem of the QoS (Quality of Service)-aware manufacturing service composition is NP-hard. Thus, the optimization remains a challenging research issue, especially in the situation of large-scale manufacturing service data which arouse a scalability problem as well. To improve both the optimization performance and scalability of the QoS-aware manufacturing service composition, this paper proposes a scalable and optimal QoS-aware manufacturing service composition approach via business process decomposition. Specifically, the service composition process is decomposed by using a refined process structure tree (RPST). Moreover, an optimized service composition is achieved layer by layer based on the refined process structure tree in a bottom-up manner. For the atomic tasks or the compound tasks in the same layer of RPST, the corresponding QoS-aware service selection is optimized by calculating Skyline services, which can be carried out in parallel if necessary. When the optimization arrives at the root node, the complete service composition plans are derived. In our approach, the optimal manufacturing service candidates are picked out stage by stage. In this way, both the optimality and scalability of the whole approach can be guaranteed. Extensive experiments are conducted to verify the optimality and scalability of our approach.