Because of their high toxicity and widespread distribution, the reliable selective quantification of alkyl and aryl species containing mercury, tin, or lead has been one of the goals of speciation analysis in recent years. Since becoming commercially available, GC-MIP-AED has been one of the most-used tools in this work. In this paper, the value and limitations of GC-MIP-AED for the speciation of Hg, Sn, and Pb compounds in environmental samples are reviewed and compared with the analytical characteristics of other hyphenated GC-based techniques. Because quantification of Hg, Sn, and Pb species by GC techniques normally requires complex sample preparation involving several steps, the effect of sample-preparation methods on the accuracy and precision of the results is discussed. Finally, we describe the current status of a rapid, low-cost GC-MIP-PED system specifically designed for routine quantification of Hg, Sn, and Pb species in environmental control laboratories.