The accurate and efficient extraction of urban areas is of great significance for better understanding of urban sprawl, built environment, economic activities, and population distribution. Night-Time Light (NTL) data have been widely used to extract urban areas. However, most of the existing NTL indexes are incapable of identifying non-luminous built-up areas. The high-resolution NTL imagery derived from the Luojia 1-01 satellite, with low saturation and the blooming effect, can be used to map urban areas at a finer scale. A new urban spectral index, named the Modified Normalized Urban Areas Composite Index (MNUACI), improved upon the existing Normalized Urban Areas Composite Index (NUACI), was proposed in this study, which integrated the Human Settlement Index (HSI) generated from Luojia 1-01 NTL data, the Normalized Difference Vegetation Index (NDVI) from Landsat 8 imagery, and the Modified Normalized Difference Water Index (MNDWI). Our results indicated that MNUACI improved the spatial variability and differentiation of urban components by eliminating the NTL blooming effect and increasing the variation of the nighttime luminosity. Compared to urban area classification from Landsat 8 data, the MNUACI yielded better accuracy than NTL, NUACI, HSI, and the EVI-Adjusted NTL Index (EANTLI) alone. Furthermore, the quadratic polynomial regression analysis showed the model based on MNUACI had the best R2 and Root-Mean Square Error (RMSE) compared with NTL, NUACI, HSI, and EANTLI in terms of estimation of impervious surface area. It is concluded that MNUACI could improve the identification of urban areas and non-luminous built-up areas with better accuracy.