Since entering the ‘Millennium of the cities’ omnipresent rapid urbanization has caused dramatic changes to ecosystem functions and generated huge ecological risks across city catchments. An understanding of how multiple ecosystem services are associated across complex social-ecological systems is required for urban sustainability. However, few studies have explored how the trade-offs and synergies of ecosystem service response to the traits of urbanization processes such as the variation of undeveloped-developed continuum. In this study, we took the Yangtze River Delta in China, a typical megapolis, as the case study area and quantified seven ecosystem services at a 10 km x 10 km spatial scale. We presented the spatial distribution and interactions of these services and identified whether they coexist in the form of specific cluster types. We found positive spatial autocorrelations across the study site. A significant tendency of trade-offs was detected between regulating and agricultural provisioning services, and we also spotted the possibility of both trade-offs and synergies that regulating and (different) cultural services were able to provide. Our results identified four different cluster types, and the cluster distributions are strongly associated with the urbanization levels—a tendency for urbanizing areas to witness the function shift in the certain order of ‘ecology – provision – multifunction – accessibility’. This provides a deeper understanding of the interactions among multiple ecosystem services and how they were determined by the ongoing social-ecological influences. The close connection between urbanization processes and ecosystems interact across developing and developed areas should be taken into consideration for future landscape planning.