Electron-beam evaporation was used to produce thin films of ß-dicalcium silicate. Chemical and mineralogical compositions were characterized by X-ray photoelectron spectroscopy (XPS) and grazing-angle X-ray diffraction (GAXRD), respectively. Results showthat no fractionation occurs during evaporation and isostructural condensation of the material as synthesized films have the same composition as the initial bulk material. Samples were gradually hydrated under saturatedwater spray conditions and analyzed with XPS. Polymerization of the silicate chains due to hydration, and subsequent formation of C-S-H, has been monitored through evaluation of energy shifts on characteristic silicon peaks. Quantitative analyses show changes on the surface by the reduction of the Ca/Si ratio and an increase on the difference between binding energies of bridging and non-bridging oxygen. Finally, SEM/FIB observation shows clear differences between the surface and cross section of the initial sample and the reacted sample.