Rapid urban expansion and development have resulted in the conversion of many natural green surfaces within cities to non-transpiring built-up surfaces, such as concrete and asphalt. These artificial urban surfaces cause substantial variation in land surface temperatures that affect the urban microclimate. Thus, there is the need to substantially quantify the extent of green cover loss within growing cities and its impact on surface temperatures. This study used LANDSAT data to spatially assess the extent of urban expansion and its effect on land surface temperature within Kumasi, Ghana. Subsequently, the results showed significant changes in the land cover, which had an effect on the observed land surface temperatures from 1986 to 2015. Generally, there was an overall increase in the built-up areas by 24.13% (55.81 km²) from 1986 to 2015, with a corresponding increase in the mean land surface temperature by 4.16°C. As such, there is the need for the adoption of sustainable urban planning strategies with green vegetation conservation initiatives for modern city planners. This would help reduce urban land surface temperatures while promoting clean air circulation within the city.