The phase-mineral and chemical composition of feed coals and their fly ashes (FAs) produced in four large Spanish thermo-electric power stations was characterized as a basis for multicomponent FA utilization. The feed fuels used are bituminous coals, semi-anthracites and anthracites with high detrital mineral abundance and mixed carbonate and sulphide-sulphate authigenic mineral tendency. Their mineral composition includes quartz, kaolinite, illite-muscovite, pyrite, chlorite, plagioclase, K-feldspar, gypsum, siderite, calcite, dolomite, marcasite, montmorillonite, jarosite, and ankerite. The FAs studied have aluminosilicate composition with higher concentrations of alkaline and alkaline-earth oxides than Fe oxide. Elements such as Ag, As, Ba, Cr, Cs, Li, P, Sb, Sc, Sn, Sr, Ti, V, Zn, and Zr are relatively enriched in these FAs in comparison with the respective mean values for bituminous coal ashes worldwide. The FAs consist basically of alummosilicate glass, to a lesser extent of mineral matter (with high silicate abundance and dominant oxide tendency) and moderate char occurrence. The phase-mineral composition (in decreasing order of significance) of these FAs is normally glass, mullite, quartz, char, kaolinite-metakaolinite, hematite, cristobalite, plagioclase, K-feldspar, melilite, anhydrite, wollastonite, magnetite and corundum plus 42 important accessory minerals or phases. A scheme of conventional separation procedures was applied to recover sequentially six initial and potentially useful and/or hazardous products from FAs, namely: (1) a ceramic cenosphere concentrate; (2) a water-soluble salt concentrate; (3) a magnetic concentrate; (4) a char concentrate; (5) a heavy concentrate; and finally (6) an improved FA residue. (C) 2003 Elsevier Science Ltd. All rights reserved.