Increasing human activity around the world has greatly changed the natural ecosystem and the services it provides. In the past few decades, a series of significant changes have taken place in land use/land cover (LULC) in China due to the rapid growth in population, particularly in the cities of the Zhujiang Deita. However, there have been few attempts to study the co-evolution of land use/land cover change and ecosystem service value (ESV) in the main urban area of Guangzhou. Therefore, based on Landsat TM/OLI images from 1987, 1993, 1999, 2005, 2011 and 2017, the weight vector AdaBoost (WV AdaBoost) multi-classification algorithm was utilized to extract LULC data sets, and the spatiotemporal patterns of LULC over these periods were studied. The ESV was estimated and the driving force was analysed. The effect of LULC dynamics on the ESV was evaluated. The results showed that great changes have taken place in LULC in the main urban area of Guangzhou from 1987 to 2017, of which the most significant was the large-scale expansion of the built-up area that occurred through degradation of the forest and cultivated land. The proportion of forest and cultivated land decreased from 43.12% and 34.23% to 25.88% and 12.59%, respectively. The results between periods revealed a decrease in total ESVs from 5.63 × 109 yuan in 1987 to 5.27, 4.16, 4.62, 3.76 and 4.47 × 109 yuan in 1993, 1999, 2005, 2011 and 2017, respectively. In total, ESVs decreased by 1.16 billion yuan (20.61%) from 1987 to 2017. Water supply, food production, nutrient cycling and gas regulation were the four principal ecosystem service functions that affected the total ESVs. Forest, water body and cultivated land areas played a key role in ecosystem services. Therefore, we advocate that when protecting natural ecosystems in the future land use management in Guangzhou should be prioritized.