Simulating the change in ecosystem service values (ESVs) caused by land use changes in metropolitan areas under multiple scenarios is of great significance to ensure regional ecological security and sustainable urban development. This study assessed the variations in land use and ESV in the main urban area of Hangzhou, China, from 2000 to 2020. A total of four future land use scenarios for 2030 were created using the cellular automata–Markov prediction model and ESVs were calculated for four future scenarios. The results are as follows: (1) Arable land and construction land were the most drastic types of land use changes in the main urban area of Hangzhou during the study period. From 2000 to 2020, construction land in the main urban area of Hangzhou expanded rapidly, with an increase of 46,916.82 hm2, while the cultivated land area decreased significantly by 38,396.43 hm2. (2) The ESV in the study area continuously declined from 2000 to 2020, with high-value ecosystem service areas predominantly found in forest areas and water areas. (3) The values of ecosystem services under the simulated future scenarios of natural development, rapid development, planned development, and ecological development were CNY 15.053, 14.525, 16.690, and 16.799 billion, respectively. The planned development and ecological development scenarios effectively ensure a high ESV. The results indicated that balancing various types of land use is essential to guarantee ecological security in urban development. Moreover, urban development and construction should be undertaken in areas with a low ESV. This forecasting study can serve as a key reference for policy makers regarding the urban landscape sustainability of Hangzhou City. The integrated simulation method of land use and ESV proposed in this study can shed light on the urban spatial layout and spatial regulation in urban land use planning.