The study aimed at evaluating the geochemical fractions of Zn, Pb, Cd and their bioavailability in soil in-depth and around the root of Pinus halepensis grown on heavily contaminated mine tailing in south-western Sardinia, Italy. The contaminated substrates were partly investigated in a previous study and are composed of pyrite, dolomite, calcite, quartz, gypsum, barite, iron-sulfate and iron-oxide. The geochemical fractions and bioavailability of Zn, Pb and Cd were measured through the BCR extractions method. Cadmium in the superficial contaminated substrates was mainly found in the exchangeable BCR fraction. Zinc and lead were often found in the residual BCR fraction. PCA confirmed that the uppermost alkaline-calcareous layers of mine waste were different with respect to the deeper acidic layers. We demonstrated that Pb and Zn were less present in the exchangeable form around the roots of P. halepensis and in soil depth. This can be due to uptake or other beneficial effect of rhizospheres interaction processes. Further studies will shed light to confirm if P. halepensis is a good candidate to apply phytostabilization in mine tailing.