The aim of this in vitro study was to evaluate the pH value of intact and carious dentin in primary teeth using a pH-imaging microscope (SCHEM-100, HORIBA Ltd., Kyoto, Japan). Bucco-lingual cut sections of extracted human primary teeth, which had either mild or severe dentinal caries lesions, were placed on the pH-imaging sensor of the microscope. The pH values were compared statistically by Levene's test for equality of variances and Tukey HSD multiple comparison test (p < 0.05). For both mild and severe lesions in primary dentin, the lowest pH values in the carious lesions were lower than those of intact dentin (6.6, range 6.3-6.9). There were statistical differences between the lowest pH value within the mild lesions (6.2, range 5.8-6.4) and that of the severe lesions (6.0, range 5.9-6.2) (p < 0.05). It was concluded that SCHEM-100 was able to distinguish the pH-value distribution of intact and carious dentin in primary teeth.