This paper constructs and optimizes, for the first time, the decomposition framework of inter-city outflow and export from the urban scale and analyzes the basic characteristics of China’s urban manufacturing industry’s participation in the global value chain and national value chain from the perspective of temporal and spatial evolution. The results show that the participation index of the manufacturing industry in coastal cities is higher than that in inland cities, and inland cities are more inclined to rely on the domestic value chain to obtain superior resources for the development of the manufacturing industry. The indicators of the manufacturing industry in the cities of the province show excellent performance, while the indicators of the peripheral cities show poor characteristics. At the same time, the length index of the global value chain of the coastal city manufacturing industry is also consistent with the actual development of the urban manufacturing industry in China. The performances of China’s urban manufacturing industry in participating in the global value chain and the domestic value chain are different. Under the background of the new development pattern, the effective docking of the double chains should be realized to achieve high-quality development in the manufacturing industry.