Dolomite can be used as a source of aluminosilicate to produce geopolymers; however, this approach is limited by its low reactivity. This study analyzes the viability of producing geopolymers using dolomite/fly-ash with sodium silicate and NaOH solutions (at multiple concentrations) by determining the resultant geopolymers’ compressive strengths. The dolomite/fly-ash-based geopolymers at a NaOH concentration of ~22 M resulted in an optimum compressive strength of 46.38 MPa after being cured for 28 days, and the SEM and FTIR analyses confirmed the denser surface of the geopolymer matrix. The synchrotron micro-XRF analyses confirmed that the Ca concentration exceeded that of Si and Mg, leading to the formation of calcium silicate hydrate, which strengthens the resulting geopolymers.