Land surface temperature (LST) is an essential parameter in the climate system whose dynamics indicate climate change. This study aimed to assess the impact of multitemporal land use and land cover (LULC) change on LST due to urbanization in Hefei City, Anhui Province, China. The research methodology consisted of four main components: Landsat data collection and preparation; multitemporal LULC classification; time-series LST dataset reconstruction; and impact of multitemporal LULC change on LST. The results revealed that urban and built-up land continuously increased from 2.05% in 2001 to 13.25% in 2020. Regarding the impact of LULC change on LST, the spatial analysis demonstrated that the LST difference between urban and non-urban areas had been 1.52 K, 3.38 K, 2.88 K and 3.57 K in 2001, 2006, 2014 and 2020, respectively. Meanwhile, according to decomposition analysis, regarding the influence of LULC change on LST, the urban and built-up land had an intra-annual amplitude of 20.42 K higher than other types. Thus, it can be reconfirmed that land use and land cover changes due to urbanization in Hefei City impact the land surface temperature.