Sulfate radicals (SO4•−) based advanced oxidation processes (AOPs), with high efficiency and selectivity toward degradation of refractory organic contaminants, have captured increasing worldwide attention. Here, an efficient advanced oxidation process based on SO4•− (i.e., a CRI/S(IV) process), induced by commercial reduced iron (CRI) powder-induced aqueous sulfite [S(IV)] activation for favorable degradation of refractory organics, is reported. The CRI/S(IV) coupled system efficiently decomposes rhodamine B (RhB) and 4-chlorophenol (4-CP) at weakly acidic and even neutral pHs. The distributions of active sulfur and iron species distribution in the CRI/S(IV) system were investigated and implied that HSO3−, FeHSO3+ and FeSO3+ were the main active species for S(IV), Fe(II), and Fe(III), respectively. In addition, radical quenching experiments show that both SO4•− and hydroxyl radicals (•OH) are present in this CRI/S(IV) system with SO4•− as the dominant reactive radical for contamination removal. Furthermore, this novel process surpassed both CRI/Oxone and CRI/persulfate systems towards the organic degradation. This work might provide an implication for an efficient practical route for SO4•− activation for wastewater decontamination, particularly for sulfite contaminated wastewaters with recalcitrant organic contaminants.