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The conditions under which mechanical properties of dentine are tested influence the values recorded. The aims of this study were to examine the effect of hydration on the mechanical properties of primary carious dentine and to provide information on changes in hardness and modulus of elasticity change caused by the demineralizing caries process in dentine. Three primary molar teeth with untreated carious dentine were prepared for nano-indentation tests under both wet and dry conditions. Further tests were conducted on eight primary molars with untreated carious dentine under hydrated conditions. The mechanical properties of dehydrated carious dentine increased approximately 10-fold for hardness and 100-fold for the modulus of elasticity compared with hydrated dentine. The hardness and elastic modulus of the carious primary dentine deteriorated progressively toward the lesion cavity floor, ranging from 0.001 to 0.52 GPa and from 0.015 to 14.55 GPa, respectively, and could be fitted to a simple linear relationship when plotted in logarithmic scale vs. distance. The total depth of dentine affected was around 1100 μm parallel to the tubule direction. This depth was significantly greater than observed subjectively, implying that the demineralization process is more advanced than might be suspected on simple clinical examination.