The development of a sequential extraction method for mercury in solid environmental samples is presented. The scheme recognizes and quantifies four major phase associations of mercury: "Labile mercury species", "Hg bound to humic and fulvic complexes", "elemental Hg and bound to crystalline oxides" and "Hg sulfide and refractory species". Model solids were used in this study to evaluate different extracting solutions and to determine optimum extraction conditions. Sequential and single-step extractions were conducted to evaluate the interaction among the successive steps. Different variables such as extractant concentration, time, temperature and number of extractions were optimized for each stage when necessary. The selectivity of the selected extractions was assured through experiments with natural and synthetic matrices of some specific Hg-bearing phases. The suitability of the proposed method was evaluated by using four certified reference materials from different Hg sources, physicochemical properties and total Hg content (from 0.3µgg(-1) to 33µgg(-1)). Recovery of total Hg by the sum of fractions in reference materials showed that the accuracy of the method ranges from 85 percent to 105 percent.