The dependence on the hydration rate for Alite and Belite clinker phases in the presence of a polycarboxylate superplasticizer PC SP upon addition of colloidal nano-silica CNS were monitored by means of Diffuse Reflectance Infrared spectroscopy DR-FTIR. Spectral signatures of clinker dissolution and product formation were acquired for both materials. The rates for the build-up of product vibrational band intensities were found to depend sensitively on addition of CNS. The hydration product was proposed to be calcium-silicate-hydrate C-S-H. Details in the spectral signatures were found to differ. Quantum chemical calculations were employed and found to be consistent with the interpretation that small clusters dominate the Alite C-S-H spectrum, whereas the Belite C-S-H spectrum results from extended polymers.