Experiment research of nanometer TiO2 catalytic combustion to CaO desulfurization was studied. Desulfurization effect was measured by the composition analysis of fly ash after combustion and the content of SO2 in flue gas. The effects of analytical grade CaO desulfurization by nanometer TiO2 addition, Ca/S molar ratio, nanometer TiO2 that was prepared at different conditions and combustion temperature were discussed. Desulfurization effects were compared with different coals and Ca-base agents by nanometer TiO2 addition. The reaction products wereanalyzed by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) analysis. The combustion desulfurization mechanisms of CaO by nanometer TiO2 addition were discussed. The experiment results show that nanometer TiO2 has good catalytic effect to CaO combustion desulfurization. When nanometer TiO2 was added together with CaO, the optimal addition dosage of nanometer TiO2 is 8%, Ca/S molar ratio is 2 and the combustion temperature is 850 degrees C. The desulfurization efficiency of analytical and industrial grade CaO catalyzed by nanometer TiO2 can achieve to 87.8% and 60.3%, and it increased 13.4% and 29.6% than that without nanometer TiO2. The pore diameter and surface area of different coal ashes with nano-TiO2 addition increase because of the active centers of nano-TiO2 surface which are helpful to the diffusion of SO2 and reaction of SO2 to SO3 and increase the desulphurization efficiency of CaO.