Multiple acute and chronic toxicity of arsenic species and its mobilisation from geological deposits into ground and drinking water resources are one of the greatest threats to human health. Arsenic speciation analysis, mostly done by liquid chromatography, is a challenging task which requires an intense high quality work with respect to extraction, preservation, separation, detection and validation. A growing number of As-species and low regulatory limits (10 μg/L) may require more than one speciation method preferably performed by species specific procedures and detectors. Beside As-fractionation for special application there are many selective speciation methods based on high performance separation techniques like capillary electrophoreses, gas and liquid chromatography. Both, fractionation and speciation methods are reviewed. However, the focus is on scopes and limits of ion chromatographic separations, the most frequently used methods. Based on IC-principles the methods applied are critically discussed and recommendations given which should result in more robust and reliable As-speciation.