Presented work brings results of Laser-Induced Breakdown Spectroscopy (LIBS) and Thermo-Mechanical Analysis (TMA) of coals and coal blends used in coal fired power plants all over Spain. Several coal specimens, its blends and corresponding laboratory ash were analyzed by mentioned techniques and results were compared to standard laboratory methods. The indices of slagging, which predict the tendency of coal ash deposition on the boiler walls, were determined by means of standard chemical analysis, LIBS and TMA. The optimal coal suitable to be blended with the problematic national lignite coal was suggested in order to diminish the slagging problems. Used techniques were evaluated based on the precision, acquisition time, extension and quality of information they could provide. Finally, the applicability of LIBS and TMA to the successful calculation of slagging indices is discussed and their substitution of time-consuming and instrumentally difficult standard methods is considered. (C) 2010 Published by Elsevier B.V.