In this study, the carbonation of Portland cement by direct chemical interaction with graphene oxide (GO) and reduced graphene oxide (rGO) at 7 and 28 days was examined. During the carbonation reaction, the calcium-bearing phases (calcium hydroxide, calcium silicate hydrate, and ettringite) formed calcium carbonate polymorphs, along with amorphous silica gel, gypsum, and alumina gel. These reaction products were examined using XRD (X-ray diffraction), XPS (energy-dispersive spectrometry), and FTIR (Fourier transform infrared). XRD patterns showed that the intensities of the calcium hydroxide and calcium carbonate peaks in the hydrated cement mixed with GO and/or rGO are higher than the corresponding peaks in the hydrated cement without any additives. The morphology of the reaction products was also characterized by SEM (scanning electron microscopy) measurements, which showed that a needle-like phase of calcium carbonate develops on the hydrated cement. The obtained microstructure parameters enabled the development of a more precise carbonation model.