Geopolymers are emerging construction materials with lower carbon dioxide emissions compared to the conventional cementitious materials. The knowledge of the curing process and the related pore structures are important for optimizing the properties of these materials for different applications. The curing process and final pore structure are sensitive to the amount of used water, however the specifics are unclear. The curing process and pore structures of metakaolin-based geopolymers with a narrow water-to-solid (w/s) ratio (0.59–0.66) were monitored by nuclear magnetic resonance (NMR) relaxometry and cryoporometry. The 14-day curing process was investigated by monitoring the change of T₂ and T₁ relaxation times and water signal intensity. After the curing, the pore structures were characterized by 2D T₁-T₂ correlation and T₂-T₂ exchange measurements of absorbed water. The pore size distributions (PSDs) were measured with NMR cryoporometry and compared to nitrogen physisorption and mercury intrusion porosimetry (MIP) results. We found that the relaxation times decreased as the pore structure of the geopolymers matured during the curing while the dissolution and the condensation periods of the curing were distinguished by the changes in signal amplitude reflecting the proton density. After the curing, three distinct pore sizes and connectivity between pores were identified from T₁-T₂ and T₂-T₂ spectra. Their PSDs were measured, and they were found to correspond to two different pore sizes originating from the arrangement of clusters and defective pores. In the narrow w/s ratio (0.59–0.66), the curing times were the same for all samples when cured at 24 °C while the pore sizes were observed to increase as a function of the w/s ratio.