The effects of the incorporation of sodium-free bioactive glass into glass ionomer cement (GIC) on the demineralized dentin are studied. Four experimental groups with various amounts of BAG in GIC were considered: BG0 group: 0 wt% (control); BG5 group: 5 wt%; BG10 group: 10 wt%; BG20 group: 20 wt%. The GIC surface and GIC-approximated demineralized dentin surfaces were evaluated using field emission scanning electron microscopy (FE-SEM). X-ray diffraction (XRD) analysis was performed to evaluate the chemical changes in the GIC-approximated dentin surface. In addition, a shear bond strength test was performed to evaluate the effects of BAG incorporation on the bond strength of GIC. FE-SEM analysis indicated that BAG-incorporated GICs formed distinct precipitates on their surface. Precipitates were also formed on the GIC-approximated demineralized dentin surface. It was more obvious when the amount of BAG increased. In the XRD analysis, fluorapatitie (FAP) peaks were detected in the BG5, BG10, and BG20 groups. There was no significant difference in the shear bond strength among all experimental groups. BAG-incorporated GIC precipitated FAP crystals underlying demineralized dentin surface without affecting bond strength. This study suggests the possibility of BAG as a beneficial additive in GIC.