Land surface temperature (LST) can fully reflect the water–heat exchange cycle of the earth surface that is important for the study of environmental change. There is little research on LST in the semi-arid region of Abha-Khamis-Mushyet, which has a complex topography. The study used LST data, retrieved from ASTER data in semi-arid mountain areas and discussed its relationship with land use/land cover (LULC), topography and the normalized difference vegetation index (NDVI). The results showed that the LST was significantly influenced by altitude and corresponding LULC type. In the study area, during the summer season, extreme high-temperature zones were observed, possibly due to dense concrete surfaces. LST among different types of land use differed significantly, being the highest in exposed rocky areas and built-up land, and the lowest in dense vegetation. NDVI and LST spatial distributions showed opposite trends. The LST–NDVI feature space showed a unique ABC obtuse-angled triangle shape and showed an overall negative linear correlation. In brief, the LST could be retrieved well by the emissivity derived NDVI TES method, which relied on upwelling, downwelling, and transmittance. In addition, the LST of the semi-arid mountain areas was influenced by elevation, slope zenith angle, aspect and LULC, among which vegetation and elevation played a key role in the overall LST. This research provides a roadmap for land-use planning and environmental conservation in mountainous urban areas.