To divert fly ash from hazardous waste stream to beneficial uses, this work aims to improve the solidification of fly ash as a geopolymer material by using graphene oxide (GO). The hydration precursors, morphology, elemental composition, mineralogy, chemical structure and ordering of GO-modified fly ash geopolymer were investigated by means of Raman spectroscopy, SEM/BSE, EMPA , XRD/TGA and Si-29/Al-27 MAS-NMR, respectively, to unravel the role of GO. The experimental results suggest that GO regulated the Ca/Si, Si/Al and Ca/(Si+Al) mole ratios to facilitate the formation of fly ash hydrates with improved mechanical strength, as GO showed the ability to selectively affect the distribution of different hydration precursors. GO also promoted the formation of low quartz and jennite-like hydrates. Overall, the 28-day compressive strength of fly ash geopolymer (w/b = 0.35) in this study was improved by 23% (from 33.6 MPa to 41.4 MPa) with GO admixed at 0.02% by mass of fly ash. The NMR study showed that GO improved the polymerization degree of fly ash geopolymer by increasing the total Q(3) and Q(4) Si-tetrahedrons, which suggests potential for improving the immobilization of heavy metals in fly ash.