It was recently proposed that the induction period observed during the hydration of tricalcium silicate could be explained by the build-up of ions in solution. Due to the importance of defects in this mechanism, this work describes the effect of different annealing effects on the defect structure and hydration behavior of C3S. The impact of annealing on the crystal structure was checked by X-ray diffraction and the defect structure studied by transmission electron microscopy. The hydration kinetics were followed by isothermal calorimetry of pastes. Scanning electron microscopy was used to look at the microstructure formation. It was observed that grinding created a highly deformed layer on the surface of the grains, which disappeared after annealing. The defect structure was closely related to the length of the induction period observed in pastes by calorimetry. There was no observable effect on the morphology of C–S–H during hydration, but the number of calcium hydroxide nuclei was less in pastes from annealed material.