The hydration of a mixture of tricalcium silicate and silica has been studied by Si-29 solid-state nuclear magnetic resonance, using selective enrichment of the reactants with Si-29 in order to follow and compare the behaviour of the silicon nuclei originating from either source. This approach shows for the first time that the silicon atoms from the two components are not equilibrated throughout the hydration products but are preferentially located in distinct species. In particular, from the distinctive spectra observed when the silica only is enriched, it is concluded that the part of the calcium silicate hydrate gel formed which incorporates silicon from this source has a longer chain length and a slightly better-ordered structure than the remainder. The spectra obtained with selective enrichment are interpreted in terms of a model based on a dreierkette chain structure for C-S-H.