This study reports the effect of natural dolomite addition to fly ash and the mechanical activation of this blend on the geopolymerization process. Dolomite was replaced with fly ash at 1, 3, 5, and 10 wt.%. Geopolymers were synthesized at ambient temperature using NaOH solution as an alkaline agent. The geopolymerization process, reactivity of the raw material, compressive strength, and microstructure were studied using X‐ray diffraction, Fourier‐transform infrared spec-troscopy, thermogravimetry, and scanning electron microscopy. It was shown that blending fly ash with dolomite and mechanical activation improved the geopolymer strength, especially during the early age of curing. For geopolymers prepared using a 90% fly ash + 10% dolomite blend cured for 7 d, the strengths were 8.2‐, 2.3‐, and 1.4‐fold higher than those for geopolymers prepared using 100% FA for 30 s, 180 s, and 400 s milling times, respectively. A simple method for evaluating the increments of mechanical activation, carbonate additives, and the synergistic effect in the increase in the compressive strength of the composite geopolymer is proposed.