Desulfurization performance of wasted seashells was found to be over twice as high as that of limestone, which was currently used as a desulfurizer in fluidized bed coal combustors. NaCl-doping into limestone was also found to be effective in improving the desulfurization efficiency. From X-ray diffraction (XRD) analyses of calcined seashell, limestone and NaCl-doped limestone, on the other hand, not only the calcined seashell but also the NaCl-doped limestone had strong peaks of CaO crystal, and those two materials also had high desulfurization activity. This improvement was hypothesized to be due to NaCl causing a change in the crystal structure of CaO. In order to elucidate the effect of NaCI addition on the CaO crystal structure in the incineration of CaCO3 the change of structures was simulated by means of molecular dynamics simulations of CaO. In the simulation one molecule of NaCl was exchanged into one molecule of CaO. A pair correlation functions and the distances between Ca and O atoms, which were obtained by the simulations, were compared with those from the crystal CaO. NaCl-doping affected the crystalization temperature of CaO. The crystallization temperature increased due to adding a little bit of NaCl. From the result of the pair correlation functions obtained in NaCl-doped CaO, the difference of the potential energy of NaCl from that of CaO seemed to contribute to the crystallization of the bulk of CaO. The simulation and experimental results obtained suggested that NaCl-doping contributed to crystallizing the CaO molecules.