Steelmaking slag was confirmed to be a useful fertilizer for paddy growth as it efficiently supplies Ca and Si to soil water. In addition, supplement of Fe from slag fertilizer has been expected to suppress the H2S generation in paddy soil, especially for the degraded paddy soil. However, on the basis of our previous research, the Fe dissolution ability changed with slag brands, and even some brands could dissolve Fe under paddy soil pH, the supplying ability were not high. To improve Fe dissolution, we found that among various kinds of Fe-rich mineralogical phases in slag, the CaO–SiO2–FeO glassy phase showed highest water solubility of Fe. Because the CaO–SiO2–FeO glassy phase was a quenched molten phase, its dissolution behavior may depend on chemical composition, and this is important for controlling slag composition to produce fertilizer which can easily release Fe. Therefore, in this research, the CaO–SiO2–FeO glassy phase of various CaO/SiO2 ratio, Fe2+/T–Fe ratios, and FeO contents were synthesized, and the dissolution behaviors of Fe as well as other cations from these synthetic glassy phases into an aqueous solution at pH of 5 were investigated. The result showed that the dissolution ratio of Fe increased significantly by increasing Fe2+/T–Fe ratio. An increase in FeO content of glassy phase also increased the dissolution of Fe. In addition, the Fe dissolution ratio showed a local maximum with increasing CaO/SiO2 ratio.