In this study, the features of fly ashes originating from industrial-scale high volatile bituminous coal combustion and co-combustion of coal with 10% admixture of alternative fuel SRF (solid recovered fuel) are presented, with emphasis on the organic petrographical characteristics. The organic petrographical and mineralogical data are co-evaluated with geochemical data, with the aim to provide a full classification of the studied fly ashes, as well as base information toward any potential application of this waste material, according to the recycling economy principles. By applying organic petrographical methods, the assignment of the carbon-rich residuals to the respective feed fuel, either coal or SRF, can be achieved. The obtained quantitative evaluation provides useful information regarding the combustion conditions in the stoker boiler. The analyzed fly ashes contain significant C-residuals, mostly in the form of fused, dense, and anisotropic particles, while the enrichment in sooty particles is caused due to the addition of SRF fuel. In conjunction with the moderate-low content of potential hazardous elements, the features of the contained C-residual phases suggest that these fly ashes could possibly be the subject of further studies for their applicability as soil improvements.