Trace elements are unevenly distributed and speciated throughout the cereal grain. The germ and the outer layers of the grain have the highest concentrations of trace elements. A large fraction of the trace elements is therefore lost during the milling process. The bioavailability of the remaining trace elements is very low. This is usually ascribed to the formation of poorly soluble complexes with the phosphorus storage compound phytic acid. Hence, analysis of the total concentration of trace elements in grain tissues must be combined with a speciation analysis in order to assess their contribution to human nutrition. This chapter deals with the fractionation of anatomically very different cereal tissues. Procedures for microscaling of digestion procedures are outlined together with requirements for the use of certified reference materials in elemental profiling of grain tissue fractions. Methods for extraction and analysis of complexes containing trace elements in the grain tissue fractions are described. Finally, the chapter concludes with criteria for choice of chromatographic methods and setting of ICP-MS instrument parameters.