The supply of ecosystem services is largely determined by changes in land use and cover. Here, we analysed how the supply and interactions among four ecosystem services have evolved over five decades in a mountain biosphere reserve largely dominated by human land uses. We modelled pastures for livestock, crop production, aquifer recharge and erosion prevention based on land use maps along five years. Multi-scale analyses were conducted to show the temporal evolution of the spatial patterns and interactions among those ecosystem services at three nested spatial scales (biosphere reserve, watershed and cell level). The overall increase in the supply of pastures and erosion prevention and the decline of crops and aquifer recharge were closely related to the abandonment of traditional land uses, particularly during the first decades. At finer scales, our results revealed that the cell areas with significant interactions among services (i.e. trade-offs and synergies) decreased from 1956 to 2007. Such evolution of trade-offs and synergies seemed to be driven by management decisions on land-use changes. Finally, we discussed the implications of our results in the context of ecosystem services’ optimization through management actions on land uses in mountain areas.