The structural development of a calcium (sodium) aluminosilicate hydrate (C–(N‐)A–S–H) gel system, obtained through the reaction of sodium metasilicate and ground granulated blast furnace slag, is assessed by high‐resolution 29 Si and 27 Al MAS NMR spectroscopy during the first 2 yr after mixing. The cements formed primarily consist of C–(N‐)A–S–H gels, with hydrotalcite and disordered alkali aluminosilicate gels also identified in the solid product assemblages. Deconvolution of the 27 Al MAS NMR spectra enables the identification of three distinct tetrahedral Al sites, consistent with the 29 Si MAS NMR data, where Q 3 (1Al), Q 4 (3Al), and Q 4 (4Al) silicate sites are identified. These results suggest significant levels of cross‐linking in the C–(N‐)A–S–H gel and the presence of an additional highly polymerized aluminosilicate product. The mean chain length, extent of cross‐linking, and Al/Si ratio of the C–(N‐)A–S–H gel decrease slightly over time. The de‐cross‐linking effect is explained by the key role of Al in mixed cross‐linked/non‐cross‐linked C–(N‐)A–S–H gels, because the cross‐linked components have much lower Al‐binding capacities than the noncross‐linked components. These results show that the aluminosilicate chain lengths and chemical compositions of the fundamental structural components in C–(N‐)A–S–H gels vary in a way that is not immediately evident from the overall bulk chemistry.