The distribution and dynamic changes in impervious surface areas (ISAs) are crucial to understanding urbanization and its impact on urban heat islands, earth surface energy balance, hydrological cycles, and biodiversity. Remotely sensed data play an essential role in ISA mapping, and numerous methods have been developed and successfully applied for ISA extraction. However, the heterogeneity of ISA spectra and the high similarity of the spectra between ISA and soil have not been effectively addressed. In this study, we selected data from the US Geological Survey (USGS) and Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) spectral libraries as samples and used blue and near-infrared bands as characteristic bands based on spectral analysis to propose a novel index, the perpendicular impervious surface index (PISI). Landsat 8 operational land imager data in four provincial capital cities of China (Wuhan, Shenyang, Guangzhou, and Xining) were selected as test data to examine the performance of the proposed PISI in four different environments. Threshold analysis results show that there is a significant positive correlation between PISI and the proportion of ISA, and threshold can be adjusted according to different needs with different accuracy. Furthermore, comparative analyses, which involved separability analysis and extraction precision analysis, were conducted among PISI, biophysical composition index (BCI), and normalized difference built-up index (NDBI). Results indicate that PISI is more accurate and has better separability for ISA and soil as well as ISA and vegetation in the ISA extraction than the BCI and NDBI under different conditions. The accuracy of PISI in the four cities is 94.13%, 96.50%, 89.51%, and 93.46% respectively, while BCI and NDBI showed accuracy of 77.53%, 93.49%, 78.02%, and 84.03% and 58.25%, 57.53%, 77.77%, and 64.83%, respectively. In general, the proposed PISI is a convenient index to extract ISA with higher accuracy and better separability for ISA and soil as well as ISA and vegetation. Meanwhile, as PISI only uses blue and near-infrared bands, it can be used in a wider variety of remote sensing images.