The rural–urban interface (RUI), known as the area where structures and other human developments meet or intermingle with wildland and rural area, is at present a central focus of wildfire policy and its mapping is crucial for wildfire management. In the Mediterranean Basin, humans cause the vast majority of fires and fire risk is particularly high in the proximity of infrastructure and of rural/wildland areas. RUI's extension changes under the pressure of environmental and anthropogenic factors, such as urban growth, fragmentation of rural areas, deforestation and, more in general, land use/land cover change (LULCC). As with other Mediterranean countries, Portugal has experienced significant LULCC in the last decades in response to migration, rural abandonment, ageing of population and trends associated with the high socioeconomic development. In the present study, we analyzed the LULCC occurring in this country in the 1990–2012 period with the main objective of investigating how these changes affected RUI's evolution. Moreover, we performed a qualitative and quantitative characterization of burnt areas within the RUI in relation to the observed changes. Obtained results disclose important LULCC and reveal their spatial distribution, which is far from uniform within the territory. A significant increase in artificial surfaces was registered near the main metropolitan communities of the northwest, littoral-central and southern regions, whilst the abandonment of agricultural land near the inland urban areas led to an increase in uncultivated semi-natural and forest areas. Within agricultural areas, heterogeneous patches suffered the greatest changes and were the main contributors to the increase in urban areas; moreover, this land cover class, together with forests, was highly affected by wildfires in terms of burnt area. Finally, from this analysis and during the investigated period, it appears that RUI increased in Portugal by more than two-thirds, while the total burnt area decreased by one-third; nevertheless, burnt area within RUI doubled, which emphasizes the significance of RUI monitoring for land and fire managers.