The surface anthropogenic heat island (SAHI) phenomenon is one of the most important environmental concerns in urban areas. SAHIs play a significant role in quality of urban life. Hence, the quantification of SAHI intensity (SAHII) is of great importance. The impervious surface cover (ISC) can well reflect the degree and extent of anthropogenic activities in an area. Various actual ISC (AISC) datasets are available for different regions of the world. However, the temporal and spatial coverage of available and accessible AISC datasets is limited. This study was aimed to evaluate the spectral indices efficiency to daytime SAHII (DSAHII) quantification. Consequently, 14 cities including Budapest, Bucharest, Ciechanow, Hamburg, Lyon, Madrid, Porto, and Rome in Europe and Dallas, Seattle, Minneapolis, Los Angeles, Chicago, and Phoenix in the USA, were selected. A set of 91 Landsat 8 images, the Landsat provisional surface temperature product, the High Resolution Imperviousness Layer (HRIL), and the National Land Cover Database (NLCD) imperviousness data were used as the AISC datasets for the selected cities. The spectral index-based ISC (SIISC) and land surface temperature (LST) were modelled from the Landsat 8 images. Then, a linear least square model (LLSM) obtained from the LST-AISC feature space was applied to quantify the actual SAHII of the selected cities. Finally, the SAHII of the selected cities was modelled based on the LST-SIISC feature space-derived LLSM. Finally, the values of the coefficient of determination (R2) and the root mean square error (RMSE) between the actual and modelled SAHII were calculated to evaluate and compare the performance of different spectral indices in SAHII quantification. The performance of the spectral indices used in the built LST-SIISC feature space for SAHII quantification differed. The index-based built-up index (IBI) (R2 = 0.98, RMSE = 0.34 °C) and albedo (0.76, 1.39 °C) performed the best and worst performance in SAHII quantification, respectively. Our results indicate that the LST-SIISC feature space is very useful and effective for SAHII quantification. The advantages of the spectral indices used in SAHII quantification include (1) synchronization with the recording of thermal data, (2) simplicity, (3) low cost, (4) accessibility under different spatial and temporal conditions, and (5) scalability.