Ecosystem services (ES) emerge from the complex interactions of diverse ecosystem components. In turn, the provision of ES is influenced by how they are put to use and environmental drivers such as climate change and land use change (CC-LUC). Researches into CC-LUC impacts on ES have so far focused on biophysical supply rather than ES interactions, making it difficult to design appropriate strategies for natural capital investment and the consequent ecosystem benefits for human well-being. In this study, we built networks from correlations among climatic forcing, land-use intensity and ES for the Xijiang River Basin in southern China, a rapidly urbanizing region with rich endowments of ecosystem assets. The variations in network structure were evaluated under different climate and land use projections up to 2035. We found that the CC-LUC-ES networks were more sensitive to land use change which affected the network structure either by directly influencing biophysical ES supplies or indirectly through altering ES interactions. Sustainable land-use management (i.e., ecological protection priority scenario) coupled with the RCP4.5 emission scenario showed higher improvements for both water-erosion prevention and regulating services. Whereas increasing land-use intensity (i.e., economic development priority scenario) with RCP8.5 resulted in losses of ES synergies and a more heterogenous network of greater integrity. Our approach provides a comprehensive view of the relationships among multiple ES and how they respond to CC-LUC, which can be applied to advance mechanistic hypotheses for ES variations. The results of this study can inform sustainable management strategies by regulating ES interactions in watersheds.