Wildfires increasingly threaten Mediterranean landscapes, particularly in regions like Attica, Greece, where urban sprawl, agricultural abandonment, and climatic conditions enhance the risk associated with the Wildland-Urban Interface (WUI). The Mediterranean basin, recognized as one of the global wildfire “hotspots”, has witnessed a steady increase in both fire severity, frequency, and burned area during the last four decades, a trend amplified by urban sprawl and agricultural land abandonment. This study represents the first integrated, region-wide mapping of the WUI and associated wildfire risk in Attica, the most densely urbanized area in Greece and one of the most fire-exposed metropolitan regions in southern Europe, utilizing advanced techniques such as Earth Observation and GIS analysis. For this purpose, various geospatial datasets were combined, including Copernicus High Resolution Layers, a multi-decadal Landsat fire history archive, UCR-STAR building footprints, and CORINE Land Cover, among others. The research delineated WUI zones classified into 40 categories of interface and intermix, revealing that WUI encompasses 26.29% of Attica, predominantly within shrub-dominated areas. An analysis of fire frequency history from 1983 to 2023 indicated that approximately 102,366 hectares have been affected by wildfires. Risk assessments highlighted that moderate hazard zones are most prevalent, covering 36.85% of the region, while approximately 25% of Attica is classified within moderate, high, and very high susceptibility zones. The integrated risk map indicates that 37.74% of Attica is situated in high- and very high-risk zones, principally concentrated in peri-urban areas. These findings underscore Attica’s designation as one of the most fire-prone metropolitan regions in southern Europe, presenting a viable methodology for enhancing land-use planning, fuel management, and civil protection efforts.