Interfacial tension is an important property that plays an essential role in understanding wetting behavior between refractories-molten slag-steel in the steelmaking process. Most work on interfacial tensions of molten slag system have been done to clarify the effect of surface active elements in molten metal and slag composition, but there has been little work done with respect to the slags ionic structure. In this study, the interfacial tension between molten slag and solid Fe was investigated to understand the effect of the ionic structure of molten slag on interfacial tension by using solid Fe instead of molten steel. Interfacial tension measurements in CaO-SiO2-FeO and CaO-SiO2-MnO slags were carried out at 1,773 K on interstitial free (IF)-steel substrates using the sessile drop method. The composition of the slag was varied with amphoteric oxides of either FeO or MnO at unit basicity (C/S = 1.0). Results indicated a decrease in the interfacial tension with increased amphoteric oxide additions. The ionic species of molten slags were analyzed by FT-IR and the various types of oxygen ions (O2-, O-, O-0) in the slag was determined by X-ray photoelectron spectroscopy. The silicate bonding degree and the slags ionic behavior were semi-quantitatively analyzed with respect to the slag's ionic structure model. By dissociating the slags networking structure with increased free oxygen ions, the interfacial tension decreased. Considering the ionic theory of molten slags, results indicate that the interfacial properties are directly affected by the ionic structure of the slag. This work hopes to clarify the relationship between the interfacial tension and the distribution of various oxygen ions.