Considerable interest is continuing to be shown in the speciation of metals, metalloids, and organometals due to the dependence of their toxicity and mobility on their chemical form. This review focuses on the speciation analysis of metals, metalloids, and organometals by solid phase extraction before spectrometric detection, and all aspects of analytical speciation such as determination of oxidation states and organometallic compounds. Some applications of speciation of metals and metalloids are also presented and discussed in this review. Fractionation, which is used sometimes as speciation, and chromatographic detection are not discussed. This review covers approximately the last four years (2012 March 2016), offering a critical review of the speciation of metals, metalloids, and organometals.