With the global climate change and the increasing human activities, ecology, resource and environment are facing more serious challenges. The researches about land use and land cover (LULC) and land surface temperature (LST) have become a hot and key research topic of global environmental change. In this study,Landsat TM images taken in 2000,2006 and 2010 were used to access the LULC and LST,and then the spatial distribution of LULC and LST were analyzed by using GIS and RS technology. It was found that the area of construction land increased quickly from 2000 to 2010. Areas of the farmland decreased significantly,whereas the areas of water and grassland remained stable. The areas of forestland increased slightly. Both NDVI and MNDWI were negatively correlated with the LST. Temperature-vegetation-index (TVX) method was further utilized to explore the urbanization of Nanjing City,and it was found that the percentage of vegetation coverage decreased and the LST percentage increased quickly. The change trajectory of the cluster point of different LULC types tended to a point in 2010. The change vector range was: forestland > grassland > water > farmland. It was also found that forestland and water region had the ability of alleviating the urban heat environment. The results of this study will help the urban planners to plan a suitable and livable city by increasing the area of green land and water,and by decreasing the areas of impervious surfaces.