The fast urban expansion has led to replacement of natural vegetation-dominated land surfaces by various impervious materials. This has a significant impact on the environment due to modification of heat energy balance. Timely understanding of spatiotemporal information of impervious surface has become more urgent as conventional methods for estimating impervious surface are very limited. In response to this need, this paper proposes a new index, normalized difference impervious surface index (NDISI), for estimating impervious surface. The application of the index to the Landsat ETM image of Fuzhou City and the ASTER image of Xiamen City in China has shown that the new index can efficiently enhance and extract impervious surfaces from satellite imagery, and the normalized NDISI can represent the real percentage of impervious surface. The index was further used as an indicator to investigate the impact of impervious surface on urban heat environment by examination of its quantitative relationship with land surface temperature (LST), vegetation, and water using multivariate statistical analysis. The result reveals that impervious surface has a positive exponential relationship with LST rather than a simple linear one. This suggests that the areas with high percent impervious surface will accelerate LST rise and urban heat island development.