Introduction: This study aims to analyze the influence of particles size of sol-gel derived calcium silicate particles in the setting reaction of bioactive endodontic cements. Materials and Methods: Sol-gel derived calcium silicate particles were synthesized and sieved to separate the particles in different sizes: CS400, CS200, and CS100. A commercial MTA (Control) was used as control. The particle size and the specific surface area were assessed by laser diffraction and nitrogen adsorption. The cements were prepared with water as the liquid for the reaction. The setting time was conducted according to ISO 6876, and the setting kinetics was analyzed by Fourier transformed infrared spectroscopy (FTIR) at different time points between 120s to 72h. Results: The particle size varied from 9.45µm (CS400 ) to 31.01 (Control). The higher specific surface area valuer reached 15.14g/cm2 in the CS400. The smallest particle sizes, the higher specific surface area, and the lowest setting time were found for CS400 (p < 0.05). Control presented the highest setting time (p < 0.05). The FTIR analyses showed the differences in materials structure over time, with faster hydration and crystallization for CS400. The setting kinetics was slower for Control even when compared to a sol-gel derived group with similar particle size. Conclusion: The route of synthesis and the particle size influences the setting reaction of calcium silicate-based cements. The reduction of particle size for sol-gel derived calcium silicates lead to the acceleration of the setting reaction of the produced bioactive endodontic cement.