During the rapid urbanization phase, the trade-off between ecosystem services is the most severe and also the most effective stage to implement ecological management. Exploring the natural—social driving mechanisms for trade-offs contributes to the coordinated development of the social economy and nature. Taking the typical mountainous city (Yibin) that is currently in the rapid urbanization phase and ecologically fragile as an example, utilizing a combination of difference comparison, trade-off–synergy index (TSI), optimal-parameter-based geographical detector model (OPGD), and multi-scale geographically weighted regression (MGWR), we spatially assess the nature and intensity of ES relationships and explore its social–natural driving mechanisms. Our findings reveal the following: (1) Varied geospatial patterns of four ESs—habitat quality (HQ), carbon storage (CS), soil conservation (SC), and water yield (WY)—with the greatest fluctuations in WY. (2) Significant changes in the nature and intensity of ES relationships over time, showing predominant positive synergies between WY-HQ, WY-SC, and HQ-CS, and negative synergies between HQ and SC, and trade-offs between WY-CS and SC-CS. (3) Distinct, time-varying driving factors for different ES relationships: climate and topography for WY, vegetation and topography for CS, topography and economic factors for HQ, and climate and topography for SC. Rapid urbanization has diminished the role of natural factors. (4) The regression coefficients reveal the local mechanisms of various driving factors, based on which targeted recommendations can be proposed. For instance, the establishment of interconnected small wetlands and green spaces in urban areas contributes to the enhancement of multiple ESs. The purpose of this study is to provide scientific insights into the driving mechanisms and optimizations of the key ecosystem services' relationships in areas that are currently undergoing rapid urbanization. [ABSTRACT FROM AUTHOR]