<p>It can support decision-making for formulating rational management policies to advance regional sustainable development by evaluating ecosystem services (ESs) and analyzing their relationship on the metropolitan area scale under setting various development goals in future. Hence, with a view to achieve this research purpose, a general conceptual framework was built in this paper. Selecting the Nanjing metropolitan area (NMA) for the case, this paper first quantified the spatio-temporal evolution of ESs. Next, three development scenarios (business-as-usual (BAU), economy-centered development (ECD), and ecological protection priority (EPP) scenarios) were defined. Then the spatial distribution patterns of the NMA under these scenarios were simulated. Finally, the relationship between pairs of ESs was evaluated to evaluate their trade-offs/synergy. The analysis revealed that the issue of developed land encroaching cultivated land was far more serious in the BAU and ECD scenarios, and the occupied area were 2730.00 km² and 3019.90 km², respectively. Meanwhile, the ecological land had expanded under the EPP scenario, among which the area of water body has increased by 859.62 km². Water yield had synergy relationship with other three ESs. However, nitrogen export had trade-off relationship with carbon storage/soil retention. ESs were significantly improved, and the synergy relationship between ESs became stronger in the EPP scenario, while the trade-off relationship between ESs under the BAU scenario were weaker. Therefore, plausible and effective land use management policies were presented to strengthen the sustainable development of metropolitan areas.</p>