Precast concrete, cold weather concreting, and the emerging technique of concrete additive manufacturing are applications in which the acceleration of cement hydration plays a critical role. To allow precise control of early cement hydration in these applications, a thorough understanding of the working mechanisms of cement hydration accelerators is required. This study contributes to the understanding of the mechanism by which calcium nitrate (Ca(NO3)2) influences early cement hydration. The influence of Ca(NO3)2 on the hydration of an ordinary Portland cement has been followed by isothermal calorimetry, in situ X‐ray diffraction (XRD), quantitative XRD, compressive strength testing, and the analysis of the pore solution composition. Further, the initial pore solution, the initial phase composition, and the phase composition in the fully hydrated cement have been estimated by thermodynamic calculations to corroborate the experimentally obtained results. The results indicate that Ca(NO3)2, especially at the highest analyzed dosage of 5 wt.%, enhances the formation of ettringite and a nitrate‐containing AFm phase. Furthermore, Ca(NO3)2 accelerates alite hydration. Besides the increased Ca concentration in solution, it has been found that a reduction of the Al concentration in the initial pore solution by Ca(NO3)2 possibly contributes to the accelerating effect of Ca(NO3)2 on alite hydration. [ABSTRACT FROM AUTHOR]