Satellite-derived land surface temperature (LST) reveals the variations and impacts on the terrestrial thermal environment on a broad spatial scale. The drastic growth of urbanization-induced impervious surfaces and the urban population has generated a remarkably increasing influence on the urban thermal environment in China. This research was aimed to investigate land surface temperature (LST) intensity response to urban land cover/use by examining the thermal impact on urban settings in ten Chinese megacities (i.e., Beijing, Dongguan, Guangzhou, Hangzhou, Harbin, Nanjing, Shenyang, Suzhou, Tianjin, and Wuhan). Surface urban heat island (SUHI) footprints were scrutinized and compared by magnitude and extent. The causal mechanism among land cover composition (LCC), population, and SUHI was also identified. Spatial patterns of the thermal environments were identical to those of land cover/use. In addition, most impervious surface materials (greater than 81%) were labeled as heat sources, on the other hand, water and vegetation were functioned as heat sinks. More than 85% of heat budgets in Beijing and Guangzhou were generated from impervious surfaces. SUHI for all megacities showed spatially gradient decays between urban and surrounding rural areas; further, temperature peaks are not always dominant in the urban core, despite extremely dense impervious surfaces. The composition ratio of land cover (LCC%) negatively correlates with SUHI intensity (SUHII), whereas the population positively associates with SUHII. For all targeted megacities, land cover composition and population account for more than 63.9% of SUHI formation using geographically weighted regression. The findings can help optimize land cover/use to relieve pressure from rapid urbanization, maintain urban ecological balance, and meet the demands of sustainable urban growth.