Urbanization has bloomed across Asia and Africa of late, while two centuries ago, it was confined to developed regions in the largest urban agglomerations. The changing urban landscape can cause irretrievable changes to the biophysical environment, including changes in the spatiotemporal pattern of the land surface temperature (LST). Understanding these variations in the LST will help us introduce appropriate mitigation techniques to overcome negative impacts. The research objective was to assess the impact of landscape structure on the variation in LST in the African region as a geospatial approach in Addis Ababa, Ethiopia from 1986–2016 with fifteen-year intervals. Land use and land cover (LULC) mapping and LST were derived by using pre-processed Landsat data (Level 2). Gradient analysis was computed for the pattern of the LST from the city center to the rural area, while intensity calculation was facilitated to analyze the magnitude of LST. Directional variation of the LST was not covered by the gradient analysis. Hence, multidirectional and multitemporal LST profiles were employed over the orthogonal and diagonal directions. The result illustrated that Addis Ababa had undergone rapid expansion. In 2016, the impervious surface (IS) had dominated 33.8% of the total lands. The IS fraction ratio of the first zone (URZ1) has improved to 66.2%, 83.7%, and 87.5%, and the mean LST of URZ1 has improved to 25.2 °C, 26.6 °C, and 29.6 °C in 1986, 2001, and 2016, respectively. The IS fraction has gradually been declining from the city center to the rural area. The behavior of the LST is not continually aligning with a pattern of IS similar to other cities along the URZs. After the specific URZs (zone 17, 37, and 41 in 1986, 2001, and 2016, respectively), the mean LST shows an increasing trend because of a fraction of bare land. This trend is different from those of other cities even in the tropical regions. The findings of this study are useful for decision makers to introduce sustainable landscape and urban planning to create livable urban environments in Addis Ababa, Ethiopia.