The assessment of the urban environment is a crucial area of interest for the international community, particularly for the Kingdom of Saudi Arabia. Achieving environmental sustainability is among the goals of Saudi Vision 2030. Riyadh has recently witnessed urban expansion due to population growth, which can cause negative environmental effects unless this growth is accompanied by the development of appropriate environmental regulations and controls. Therefore, this study aimed to assess the city of Riyadh’s urban environment and its relationship to urban expansion over time. The Thermal Environmental Index (TEI), consisting of five indicators (vegetation index, urban index, moisture index, dry index, and temperature index) was constructed utilizing geospatial techniques. Pearson’s correlation analysis was performed to determine the relationship between urban expansion and urban environmental conditions. The main results show that the size of Riyadh’s urban clusters doubled by 2022, increasing by 106% compared to in 2000. The results also show that, in 2000, 2013, and 2022, areas of poor environmental conditions were mainly distributed in urban areas, whereas areas with excellent and good environmental conditions were located outside of urban areas in the northern and western parts of Riyadh. Areas with good environmental conditions continued to decline, whereas areas poor environmental conditions increased from 4%, or 240 km2, in 2000 to 11% in 2022, reaching 658 km2. The correlation analysis clearly showed a very strong relationship between urban expansion and the deterioration in urban environmental conditions.