The chemical and mineralogical composition of lignite fly ash (FA) varies as a function of the prevalent conditions in both the processes of power production and lignite mining. The differentiation of the qualitative and quantitative composition of the highly-calcareous lignite fly ash, as a function of its particle size distribution, is verified in this paper. According to the results of the conducted research, a fine-grained fraction of considerable amount presents properties that obstruct the sustainable exploitation of calcareous lignite fly ash in cement industry applications. On the other hand, the same grain fraction (because of its hydraulic properties) can be utilized in other sort of applications, based on different criteria, i.e. in road constructions. The coarse-grained fraction (which reflects a low proportion to the total fly ash output) presents the same undesired characteristics as well. Rather, the intermediate grain fraction (75150 m) presents the highly desirable properties when fly ash is utilized as a pozzolanic additive. In addition, the mechanism of the formation of the intermediate grain fraction strongly prevents the factors that cause the variation of fly ash-quality. It is therefore the optimum part of the whole amount of lignite FA, to be utilized as additive in cement manufacturing. The outcomes of this paper will hopefully contribute towards the crucial goal of the expansion of the utilization of calcareous lignite fly ash by proposing a more effective way of using this material, basically by taking advantage of its fundamental chemical and mineralogical properties