The present work systematically investigates the influence of silica fume and organosilane addition on the hydration dynamics and the capillary pore formation of a cement paste. The cement samples were prepared with two water-to-cement ratios with increasing amounts of silica fume and of (3-Aminopropyl)triethoxysilane (APTES) organosilane. Low-field 1H nuclear magnetic resonance (NMR) relaxation measurements were performed during the hydration of the samples and after hydration, in order to reveal the dynamics of water molecules and the pore distribution. Increasing concentrations of silica fume impact the perceived hydration dynamics through the addition of magnetic impurities to the pore solution. However, there is a systematic change in the capillary pore size distribution with an increase in silica fume concentration. The results also show that the addition of APTES majorly affects the hydration dynamics, by prolonging the dormancy and hardening stages. While it does not influence the pore size distribution of capillary pores, it prevents cyclohexane from saturating the capillary pores.