Knowledge as to the speciation of elements in incineration residues is important for the successful management and utilization of the residues and for modelling and predicting their leaching behavior. As part of a larger research effort on speciation in combustion residues, ESP ash from a Canadian MSW waste-to-energy facility was subjected to a number of analytical and spectroscopic techniques to identify element speciation. The intent of this effort was to evaluate the utility of various techniques and compare speciation information provided by each method. It is concluded that a variety of methods are needed to better understand speciation.