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Although research on the natural ventilation of single-sided buildings is progressing, research on the natural ventilation of the Mogao Grottoes, which have special shapes and structures, is relatively limited. The purpose of this paper is to develop a correlation for calculating the natural ventilation rates of such grottoes. Field experiments were carried out on two typical caves to measure their meteorological parameters and natural ventilation rates to verify the validity of the proposed correlation. The results show that our correlation has good reliability and stability when predicting the natural ventilation rates of the caves. First, the new correlation has a small average deviation of 16.35%. The average deviations in the natural ventilation rates predicted by seven established correlations are as low as 17.85% and as high as 59.39%, revealing a large gap compared with the correlation proposed herein. Second, the maximum deviation in the outputs of the proposed correlation is only 7.70% between each case. Finally, a comparison between the calculated results and the values measured in Cave 328 shows that the correlation is also suitable for large-volume caves. The developed correlation provides theoretical support and a scientific method for preventive protection and a quantitative analysis method for the study of natural ventilation in caves.