Technological innovation capacity is a powerful driving force to promote the adjustment and update of industrial structure, there is a healthy interaction relationship of interrelation and mutual promotion between the two. On the basis of carefully constructing the evaluation index system of technological innovation ability and industrial structure optimization and upgrading, this article uses entropy method and coupling coordination degree model to deeply analyze and discuss the coupling coordination degree relationship between the two, based on time series data from 1995 to 2015. Analysis results show that, during the period of 1995-2015, especially in the new century, the comprehensive evaluation index of China's technological innovation capability and the optimization and upgrading of industrial structure, and the coupling coordination degree between them have generally shown a steady upward trend. The coupling coordination degree increased from 0.323 in 1995 to 0.643 in 2015, from a serious disorder to a primary coordination state, but the overall coupling coordination degree is still low. In order to better promote the coordinated development between the two, which puts forward some countermeasures and suggestions.