Reaction behaviors of sulfur and iron compounds in sodium aluminate solutions were investigated. The results show that iron compounds can remarkably remove the S2 but cannot get rid of S2Oc2-, SO^2- and SO4^-2 in sodium aluminate solutions. The removal efficiency of S^2- using ferrous compound and ferric compound can reach 86.10% and 92.70% respectively when the iron compounds were added with a molar ratio of 2:1 compared with the sulfur in liquors at 100℃. Moreover, several same compounds are formed in those two desulfurization processes with ferrous or ferric compounds, including erdite, hematite, amorphous ferrous sulfide, polymerized sulfur-iron compounds and ferric sulfate. The major difference between these two processes is that the erdite generated from ferrous compounds at the initial reaction stage will convert to a sodium-free product FeS2 at the subsequent stage.