Nowadays in Poland around 18 mln tons of energy wastes are produced every year. The utilization method of wastes depends principally on their physicochemical properties. Siliceous fly ashes which have pozzolanic properties which advantageously influence on cement properties, are mainly used in production of cement. The results of studies of the phase composition of the different grain classes of the siliceous fly ash were presented in this article. The minerals: mullite and quartz as well as magnetite, hematite and calcite were identified on the base of thermal analysis, mikroscopic observation and X-ray diffractometry examination. Significant participation in the composition of investigated fly ashes have also fragments of unburned coal. They present different morphological forms depend on the porosity degree. The following forms were distinguished: cenospheres, networks, inertynite massive and porous, detritus. Porous particles accumulate mainly in the coarser grain class and are represented primarily by cenospheres and networks. Their content may have an adverse effect on any further applications of fly ash, so as it is necessary to separation of this class. This will reduce water demand and increase the freeze-thaw resistance of mortar and concrete containing fly ash.