This study explored the effect of nanofibrillated celluloses (CNF), namely 0%, 0.05%, 0.1%, and 0.15% of binders weight, on the hydration, rheology, pore structure, and mechanical properties of ultra-high ductility cementitious composites (UHDCC). The hydration kinetics were conducted with different CNF contents using isothermal calorimetry (IC), showing a retardation effect of CNF on the early hydration of UHDCC matrices at 70 h due to the absorption of CNF on the surface of cement particles. Then, thermogravimetric analysis (TGA) demonstrated that CNF improved the degree of hydration at 28 days due to the formation of the CNF transport of water into unhydrated cement cores. The two rheological parameters, namely the yield stress and plastic viscosity, of the fresh UHDCC matrices increased with the increasing CNF contents. Low-field nuclear magnetic resonance (LF-NMR) analysis, as a non-destructive method, proved that the addition of CNF could reduce the porosity of UHDCC and refine its pore size distribution, and the 8.9–46.1% enhancement in the compressive strength of corresponding specimens was found. Notably, CNF could increase the tensile initial cracking stress by 91.2% and tensile stress by 30.8% of UHDCC, and maintain or increase its over 8% of tensile strain-hardening capacity. The flexural tests also were found a 54.6% increase in the initial stress and a 14.8% increase in the peak stress. As a preliminary, CNF shows crucial promising as a greener nanomaterial to improve the strength and ductility of UHDCC.