Man-made deposits of fly ash (FA)—a solid by-product of coal combustion—accompany practically every thermal power station and many industrial plants. The total annual production of FA worldwide is about seven–eight hundred million tons, of which less than one third is recycled. The accumulated FA has become a problem for the environment due to its heavy metal content, which can be leached out. The mineral composition of FA is mainly represented by the glass phase and also by quartz, mullite, magnetite and other minerals. In the last decade, intensive studies have been carried out on the use of FA for the preparation of geopolymer materials. Due to their energy savings, environmentally friendly processing and high physical-mechanical properties, geopolymers are gaining attention in the construction industry as a potential replacement for Portland cement. In this work, we focused on the effect of natural dolomite addition to FA and mechanical activation of this blend on the geopolymerization process. The influence of dolomite dosage and duration of mechanical activation in a planetary mill on the reactivity of the blend in relation to NaOH solution and on the geopolymer compressive strength was studied.