The Almadén area is an exceptional case of mercury concentration in the world, where cinnabar is the predominant mineralised form. Mining activities have been carried out over the past two thousand years and once this activity is concluded, a restoration of the environment is necessary for the affected areas. That implies the selection, optimisation and application of the most appropriate techniques focused on the recovery of contaminated areas. Phytotechnology is one of the proposed techniques, which considers the use of plants due to the low environmental impact and their proved efficiency. In this framework, it is necessary to study the behaviour of mercury in the soil-plant system and to determine the mercury absorption capacity of the different Almadén plant species. Therefore, field and laboratory studies have been carried out to determine the easily available forms of mercury in ten test plots in the Almadén area and the resulting data is related to the mercury accumulation in different plant species of the studied territory. Special attention is given to the easily available forms of mercury in the analysed soils and used as the transfer factor for the Hg-availability index that relates the amount of mercury in a plant with the total amount of mercury in a soil and with the easily available forms. The result of this experimental work is selecting the plant species suitable to be used in a future implementation of phytotechnologies in this area.