This study employed an in-air micro-proton-induced X-ray/gamma-ray emission system to assess the effectiveness of fluoridecontaining materials (FCMs) incorporating calcium in preventing root caries. Dentin surfaces of human third molars were coated with one of three FCMs: fluoride-releasing glass-ionomer cement (F7) and experimental materials in which half (P1) or all (P2) of the strontium in F7 was replaced with calcium. Dentin without FCM coating served as the control. Specimens were immersed in saline at 37°C for 1 month, sectioned, and then demineralized. Calcium loss after demineralization was lower in the Ca-substituted groups than in the Ca-unsubstituted groups (p<0.05). Calcium loss was negatively correlated with fluoride uptake (p<0.01). In the F7, P1, and P2 groups, the retraction of the dentin surface was significantly suppressed as compared with the control group. FCMs incorporating calcium improved the acid resistance of root dentin and could help prevent root caries.