The chapter exposes how a sound methodology can be instrumented to both, biogeochemically speciate heavy metal (HM) polluted mine wastes and soils, and to develop solid strategies to agriculturally stabilize and remediate HM-polluted terrestrial environments. Using single- and sequential extraction procedures, polluted environments can be chemically speciated to successfully remediate impacted sites. Once metal(loid) toxic levels are determined, common amendments (compost, P-fertilizers, lime, gypsum) can be added to abate HM levels, and to re-sustain vegetation, based on bioassay results of HM-sensitive plants. The approach addresses first: a) a discussion of concepts and relevant chemistry that apply to study mine tailing materials and soils, via single or multiple HM-fractionation schemes; b) characterizing chemically mine tailings and soils, in terms of the metal(loid)-sorption-complexing affinities, and c) creating a “fertile environment” by agriculturally reconditioning the HM-polluted acidic mine waste to allow the vegetation regrowth, based on bioassay test performance. Results of two successful cases of study are included; one showing the use of single extraction procedures to evaluate phytoavailable/toxic HM levels to agriculturally remediate polluted sites, and another showing the role of sequential extraction procedures to discriminate heavy metal(loid)s of a spill from other metal deposits of the same ore.