Advanced preparation techniques open new ways for SEM and X-ray diffraction (XRD) investigations on hydrating cementitious systems. In this paper the early time hydration of Portland cement is studied with advanced cryo scanning electron microscopy techniques in combination with in situ X-ray diffraction and heat-flow calorimetry. The application of preparation techniques and analytical methods to Portland cement hydration are presented and discussed. Some aspects of hydration reactions are focused. The reaction products of the first minutes, changes in ettringite morphology, AFm formation during the deceleration period and the visualisation of C-S-H microstructures were special points of interest._x000D_
X-ray diffraction analyses and Cryo-SEM images gave essential information about phase development, reaction kinetics, microstructure and morphology of hydration products. Portlandite, AFt and AFm phases were detected by in situ XRD. Cryo-SEM analyses enabled high resolution imaging and EDX-analyses of cement particles and reaction products. The results of the different analytical methods were compared to obtain detailed information about crystallisation processes and microstructural development during the first three days of Portland cement hydration.