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A systematic study of geopolymers by 29Si and 27Al MAS NMR has been carried out in an attempt to understand polymer structural details. 27Al MAS NMR data shows that transient aluminium species are formed during the reaction of metakaolin with NaOH. Interaction of silicate anions with the aluminium sites of metakaolin was evident during the synthesis of geopolymers as observed from low field shift of 29Si MAS NMR resonance lines of silicate centres. As the reaction progresses, the coordination of aluminium (IV, V and VI) in metakaolin changes almost completely to IV. 29Si MAS NMR of selected compositions of the ternary system of sodium silicate, metakaolin and aqueous alkali reveals that geopolymerisation occurs in a distinct compositional region. At high alkalinity [> 30% (mol/mol) overall Na2O content], connectivity of silicate anions is reduced, consistent with poor polymerisation. At low alkalinity [<10% (mol/mol) overall Na2O content], a clear 29Si NMR resonance line due to unconverted metakaolin is observed. NMR spectra were recorded from a series of samples with a fixed Na2O content (20 mol%) and varied SiO2/Al2O3 ratio to observe aluminium substitution in the cross-linked silicon tetrahedra of polymer network. Aluminium insertion into the silicate network is confirmed from the observed 29Si NMR shift as a function of Si/Al ratio. The identification of the presence or absence of metakaolin in the cured geopolymer product is not possible even by 29Si NMR as the signal from metakaolin is indistinguishable from a broad 29Si NMR peak consisting of many resonance lines from the network of cross-linked silicon/aluminium tetrahedra. In an attempt to identify metakaolin signal, we prepared geopolymers with higher SiO2/Al2O3 molar ratios. Since aluminium substitutions in the silicate tetrahedral network are decreased, this results in better-resolved 29Si NMR lines. The 29Si NMR signal due to metakaolin is then distinguishable in the spectra of cured products in a series of samples with 3 to 11 mol% metakaolin. These results indicate that a geopolymer structure is a network of silicon/aluminium tetrahedra with some presence of unreacted metakaolin. The silicon/aluminium tetrahedra might have connectivity ranging from 1 to 4.