In multielement EDXRF analysis of very complex unknowns, some problems in data evaluation may be simplified if one can take into account a priori information on the properties of the incident and detected radiations, and also available data on the matrix of the sample. The number of variables can be drastically shortened in the LSM procedures in this case. One of the best examples of complex unknowns is the determination of the rare earth element content of ores, and most recently in samples of high temperature superconductors (HiTc).