We present a new ²⁹Si NMR–based approach to analyze the structure of mesoporous silicates (MCM-41, MCM-48, SBA-15, SBA-16). Quantifying Qⁿ (n = 0–4) contributions in the NMR spectra provides deeper insight into silica condensation and hydroxylation. https://doi.org/10.1039/D5CP03966E