Vanadium is an abundant element in the environment and is widely used in industry. V(V) as vanadate is more toxic than V(IV) as vanadyl ion. This article illustrates the requirements for V speciation and reviews the analytical methods applied to such studies including hyphenated systems such as liquid chromatography or electrophoresis coupled to atomic absorption spectrometry (AAS) or inductively coupled plasma mass spectrometry (ICP-MS).