Abstract: Based on the multi-regional input-output table at the provincial level in China from 2012 to 2017, this paper constructs the value chain index framework of “participation degree-complexity level-production location”, and analyzes the agricultural participation degree of western regions in national value chain and its production location. The main conclusions are as follows, compared with participation degree in value chains of other regions, the forward participation index of agricultural participation in the eastern value chain of western provinces is significantly higher, the backward industrial linkages of most western provinces with internal and external regions are increasing, and the production length in both forward and backward of western regions’ participation in national value chain has shortened. During the research period, the position of western regions in the national division of labor network has changed from relatively upstream to downstream; the same is true in the eastern regions. While in the northeast regional division of labor network, it is in a relatively upstream position. Therefore, we should promote cross provincial and cross regional industrial cooperation along the industrial chain, improve the science and technology level of agriculture, extend the length of agricultural value chain, and form a large circulation pattern of domestic agricultural industry chain.