Mining operations generate sediment erosion rates above those of natural landscapes, causing persistent contamination of floodplains. Riparian vegetation in mine-impacted river catchments plays a key role in the storage/remobilization of metal contaminants. Mercury (Hg) pollution from mining is a global environmental challenge. This study provides an integrative assessment of Hg storage in riparian trees and soils along the Paglia River (Italy) which drains the abandoned Monte Amiata Hg mining district, the 3rd former Hg producer worldwide, to characterize their role as potential secondary Hg source to the atmosphere in case of wildfire or upon anthropic utilization as biomass. In riparian trees and nearby soils Hg ranged between 0.7 and 59.9 μg/kg and 2.2 and 52.8 mg/kg respectively. In trees Hg concentrations were below 100 μg/kg, a recommended Hg limit for the quality of solid biofuels. Commercially, Hg contents in trees have little impact on the value of the locally harvested biomass and pose no risk to human health, although higher values (195–738 μg/kg) were occasionally found. In case of wildfire, up to 1.4*10−3 kg Hg/ha could be released from trees and 27 kg Hg/ha from soil in the area, resulting in an environmentally significant Hg pollution source. Data constrained the contribution of riparian trees to the biogeochemical cycling of Hg highlighting their role in management and restoration plans of river catchments affected by not-remediable Hg contamination. In polluted river catchments worldwide riparian trees represent potential sustainable resources for the mitigation of dispersion of Hg in the ecosystem, considering i) their Hg storage capacity, ii) their potential to be used for local energy production (e.g. wood-chips) through the cultivation and harvesting of biomasses and, iii) their role in limiting soil erosion from riparian polluted riverbanks, probably representing the best pragmatic choice to minimize the transport of toxic elements to the sea.