The change of regional land use structure has important influence on the stability of ecosystem structure and function. As a typical representative of resource-based cities in central of China, original land use structure was changed because of industrial transformation and upgrading in Taiyuan, which has become a key link in ecological environment construction. Using the Environment for Visualizing Images (ENVI), this paper calculates the ecological quality metrics of Taiyuan in the process of industrial transformation and upgrading, and explores the response of ecological quality in Taiyuan to the spatiotemporal evolution of land use structure. The results show that: (1) From 2003 to 2018, the proportion of urban construction land in east and south of Taiyuan continued to increase. (2) The ecological quality of Taiyuan improved generally. The most obvious improvement was achieved in the Fenhe River Valley. Some parts of the valley changed from strongly bad area (RSEI: 0.2–0.4) to strongly good area (RSEI: 0.8–1.0). (3) The ecological quality in Taiyuan was distributed unevenly in space. In 2013, the ecological quality in the south was poorer than that in 2003 and 2008. However, the ecological quality in that region showed a significant rebound in 2018. The research results shed important new light on urban land use structure, ecological quality evaluation, and formulation of ecological protection policies.