Rapid urbanization of Korea was an unprecedented example in the world and urban population increased significantly. As a result, unbalanced distribution of population is serious problem in Korea because approximately 50% of the population is concentrated in the capital area that is 10% of nation's territory, thereby occurring various urban problems including UHI. Hence, Sejong Special Autonomous City was inaugurated officially on 2 July 2012 in order to decentralize population of capital area and induce more balanced regional development. The Sejong City has been changed drastically over a period of years as developed practically since the late 2000's and is expected to have new problems of urbanization. The land cover change due to urbanization is the main cause of UHI that urban area is significantly warmer than its surrounding areas and UHI is not only affecting urban climate change but also natural environment. So the purpose of this research is to analyze level of urbanization and UHI effect and to provide the correlation analysis between Land Surface Temperature and spectral indices. To achieve this, satellite imagery from LANDSAT were used. NDVI, NDBI, and UI were calculated using red, near-infrared, mid-infrared (0.63μm-1.75μm) images and LST was retrieved utilizing thermal infrared (10.4μm-12.5μm) image. Based on each index and LST, Changes of NDVI, UI and UHI through TVI were analyzed in Sejong City. UHI effect increased around newly constructed multi-functional administrative city, the correlation between LST and NDVI was negative and UI was strong positive.