Cement has been selected for wastes immobilization as a simple, low temperature and low cost process for decades. The mechanical and immobilization properties of cement are mainly decided by cement hydration process, especially in the first 24 hours. Previous methods for studying the cement hydration are those include isothermal calorimetry, continuous monitoring of chemical shrinkage, in situ quantitative X-ray diffraction, nuclear magnetic resonance spectroscopy (NMR), quasi-elastic neutron scattering (QENS) and small angle neutron scattering (SANS). Few available in-situ imaging methods were successfully used for net rate study of cement hydration. In this Ph.D. research, innovative imaging techniques such as X-ray computed tomography (XCT) combined with 2D SEM-BSD analysis were combined to study the microstructure and phase change of cement or cement & SrCl2 mixture during hydration. Digital Volume Correlation (DVC) and Digital Image Correlation (DIC) were applied to study the chemical volume shrinkageand drying shrinkage of cement samples during hydration. The effects of SrCl2 simulating the radioactive nuclide from nuclear waste on cement hydration were studied by XRD and ICP-AES techniques. These studies verified that the hydration net rate could be characterised by XCT imaging techniques and the volume shrinkage of cement or cement& SrCl2 mixture during hydration could be characterised by the DVC and DIC techniques.