The process of urbanization exacerbates the urban heat island phenomenon. In order to reasonably identify urban functional zones, and reveal the influence of buildings on land surface temperature (LST). Guiyang, a multi-mountainous city in China, was taken as the research area, Open Street Map (OSM) and land use type data were used to identify urban functional zones. Subsequently, the correlation between urban building morphology metrics and LST was analyzed using Pearson correlation and boosted regression tree (BRT) model. The results showed that: (1) There were significant differences in LST among different urban functional zones. (2) The relative contribution value of building density (BD) to land surface temperature was high, and it significantly exacerbated the urban heat island effect across all urban functional zones, with the maximum impact on LST reaching 2.5 °C in Utility zone. (3) Mean building height (MBH), Southerly wind speed (S_Wind speed) and Landscape shape index of building (LSI_Building) had the effect of alleviating thermal environment, and the mitigation degree of land surface temperature was the highest in Residential zone and Ecological zone, reaching 0.6 °C, 0.8 °C and 2.0 °C, respectively. This study enhances our understanding of the relationship between urban functions and LST, providing valuable insights for mitigating the urban thermal environment and promoting sustainable development.