Toxicity of antimony depends on the species which is present in the environment, Sb(III) being more toxic than Sb(V), and methylated species of antimony being less toxic than the inorganic salts. Two of the most used AAS techniques for the determination of antimony are electrothermal atomization (ETAAS) and hydride generation technique (HGAAS). For the speciation of antimony, a combination of separation techniques with atomic spectrometric techniques is used. In the present article, AAS techniques and their combination with separation techniques for the determination and speciation of antimony in environmental samples are reviewed.