Chromatographic separation, such as gas chromatography (GC) and high-performance liquid chromatography (HPLC), coupled to an element-specific detection technique such as atomic spectrometry, forms an extremely powerful analytical system for the direct speciation and determination of metals, metalloids and organometallic compounds. The use of atomic spectrometric detection is developing particularly fast. Almost every mode of atomic spectrometry including absorption emission, and fluorescence, has been utilized. The sensitivity of these systems is commonly at the picogram to nanogram level. With these techniques, many of the highly toxic organometals, such as alkyllead and butyltin species, have been identified and determined for the first time in air, water, sediment and fish samples. This paper discusses the capabilities of gas and liquid chromatography, different modes of atomic spectrometric detection, and recent developments of these analytical systems including interfacing techniques between component instruments.