Niobium oxide (Nb2O5) is a semiconductor that exhibits photocatalytic properties, making it potentially valuable in addressing air pollution, self-cleaning, and self-disinfection in cement-based materials (CBMs). Therefore, this study aimed to evaluate the impact of different Nb2O5 concentrations on various parameters, including rheological characteristics, hydration kinetics (measured using isothermal calorimetry), compressive strength, and photocatalytic activity, specifically in the degradation of Rhodamine B (RhB) in white Portland cement pastes. The incorporation of Nb2O5 increased the yield stress and viscosity of the pastes by up to 88.9% and 33.5%, respectively, primarily due to the larger specific surface area (SSA) provided by Nb2O5. However, this addition did not significantly affect the hydration kinetics or the compressive strength of the cement pastes after 3 and 28 days. Tests focusing on the degradation of RhB in the cement pastes revealed that the inclusion of 2.0 wt.% of Nb2O5 was insufficient to degrade the dye when exposed to 393 nm UV light. However, an interesting observation was made concerning RhB in the presence of CBMs, as it demonstrated a degradation mechanism that was not dependent on light. This phenomenon was attributed to the production of superoxide anion radicals resulting from the interaction between the alkaline medium and hydrogen peroxide.