Abstract: The research is based on evolutionary economic geography, and analyzes the theoretical mechanism of the relationship between technological innovation in central cities and the industrial structure and division of labor in urban agglomerations from the three dimensions of micro-enterprises, meso-level industries, and macro-regions. On this basis, the study examines the U-shaped relationship between technological innovation in central cities and the advanced industrial structure of urban agglomerations through a nonlinear fixed effect model, and further innovatively uses historical dimension instrumental variables (quantified data from Chinese historical officials, data from ancient Chinese city walls) ) Carry out the endogenous test and identification of the technological innovation of the central city, and then use the threshold effect and the intermediary effect model to explore the structural change points of the technological innovation of the central city and the influence mechanism of the industrial division of labor. The study found: First, the technological innovation of central cities presents a U-shaped effect on the advancement of the industrial structure of urban agglomerations. When the number of patent applications for technological innovation in central cities exceeds 14,555, it will play a positive role in the optimization and upgrading of the industrial structure of urban agglomerations. Second, the technological innovation of the central city promotes the specialization and related diversification of the industrial layout of the urban agglomeration, and inhibits the irrelevant diversification of the industry. The technological innovation capital and labor resources of the central city take the technological innovation capital and labor resources as the main path to promote the division of labor in the industrial layout.