& Key message Trees outside forests (TOF) have crucial ecological and social-economic roles in rural and urban contexts around the world. We demonstrate that a large-scale estimation strategy, based on a two-phase inventory approach, effectively supports the assessment of TOF's diversity and related climate change mitigation potential. & Context Although trees outside forest (TOF) affect the ecological quality and contribute to increase the social and economic developments at various scales, lack of data and difficulties to harmonize the known information currently limit their integration into national and global forest inventories. & Aims This study aims to develop and test a large-scale estimation framework to assess ecological diversity and above-ground carbon stock of TOF. & Methods This study adopts a two-phase inventory approach. & Results In the surveyed territory (Molise region, Central Italy), all the attributes considered (tree abundance, basal area, wood volume, above-ground carbon stock) are concentrated in a few dominant species. Furthermore, carbon stock in TOF aboveground biomass is non-negligible (on average: 28.6 t ha −1). Compared with the low field sampling effort (0.08% out of 52,796 TOF elements), resulting uncertainty of the estimators are more than satisfactory, especially those regarding the diversity index estimators (relative standard errors < 10%). & Conclusion The proposed approach can be suitably applied on vast territories to support landscape planning and maximize ecosystem services balance from TOF.