Urban development in developing regions increases ecological and environmental pressures. Few annual ecological studies have been conducted on tourist-oriented cities. Guilin is famous as an international tourist destination in Chine. Analyzing its coupling coordination between urbanization and ecology is vital for subsequent sustainable development. This paper constructed a night-time light index (NTLI) based on DMSP/OLS, NPP/VIIRS night-time light data in response to these problems. The remote sensing ecological index (RSEI) model was established in this study by using four indexes: greenness, wetness, dryness and heat. The coupling coordination degree model (CCDM) was built. From the dynamic time-series changes of CCDM, the urban development and ecological environment of the urban area of Guilin, from 2000 to 2020, were analyzed. The results showed that the urban area of Guilin’s urbanization had developed rapidly over the past 20 years. NTLI in 2020 was 7.72 times higher than in 2000. The overall ecological quality of the main urban area of Guilin has improved significantly, while local ecological pressure in Lingui District has increased. CCDM has shifted from low to high coupling coordination, and the relationship between urban development and the ecological environment has improved. The method of annual spatial-temporal analysis of urban ecology in this paper can be applied in similar studies on other cities, and the results obtained for Guilin have reference value for future urban planning and environmental protection work.