With the deepened economic globalization, international division has evolved into value chain level. This paper investigates the influence of technological innovation on export structure from the perspective of production value chain, building a mathematical model to derive and analyze the positive effects of scientific and technological innovation on the status of production value chain. This paper also takes econometric methods to test the relationship factors between export structure optimization and decision factors, which confirms the positive impact of technological innovation on the export structure from the perspective of value chain. At last this paper puts forward policy recommendations: to play a key role of technological innovation and build new foreign trade pattern, both import and export are good; to explore constructing own leading global industry value chain and achieve export structure optimization under new international standards; to optimize the allocation of human resources and play a central role of human capital for technological innovation and foreign trade transformation.