AAS technique applications for the determination of organomercurials in environmental samples (water, soil, sediment, sludge, and air) are reviewed. The decomposition techniques used for sample treatment prior to the determination of total mercury by AAS technique are described. The speciation procedures for organomercurials by selective extraction, biological and chemical speciation and combination of separation techniques (GC, HPLC, IC) with AAS techniques for speciation of organomercurials in environmental samples have been presented.