It is known that while many elements are considered essential to human health, many others can be toxic. However, because the intake, accumulation, transport, storage and interaction of these different metals and metalloids in nature is strongly influenced by their specific elemental form, complete characterization of the element is essential when assessing its benefits and/or risk. Consequently, interest has grown rapidly in determining oxidation state, chemical ligand association, and complex forms of a many different elements. Elemental speciation, or the analyses that lead to determining the distribution of an element's particular chemical species in a sample, typically involves the coupling of a separation technique and an element specific detector. A large number of methods have been developed which utilize a multitude of different separation mechanisms and detection instruments. Yet, because of its versatility, robustness, sensitivity and multi-elemental capabilities, the coupling of liquid chromatography to inductively coupled plasma mass spectrometry (LC-ICP-MS) has become one of the most popular techniques for elemental speciation studies. This review focuses on the basic principles of LC-ICP-MS, its historical development and the many ways in which this technique can be applied. Different liquid chromatography separations are discussed as well as the factors that must be considered when coupling each to ICP-MS. Recent applications of LC-ICP-MS to the speciation of environmental, biological and clinical samples are also presented.