The effects of nano-TiO2(NT) on microstructures and mechanical properties of cement mortars were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), and mercury intrusion porosimetry (MIP). Results show that 3% NT can remarkably increase the tensile/flexural strengths (i.e., the toughness is improved) and promote the precipitation of AFt crystal. The flexural and tensile strengths have significant positive correlation to the formation amount of AFt. The pores of mortars can be significantly refined and shift to harmless pores by controlling the growth of CH crystal and increasing the hydration reaction rate. The durability of cement-based materials is discussed by testing their water absorption and water-vapour permeability. Results show that the addition of 3% NT can decrease the water absorption ratio by 40–65%, water absorption coefficients by more than 40%, and water-vapour permeability coefficients by 43.9%, indicating that 3% NT can effectively improve the compactness and durability of cement-based materials.