Recently, the advanced oxidation processes (AOPs) based on sulfate radicals (SRs) for organics degradation have become the focus of water treatment research as the oxidation ability of SRs are higher than that of hydroxyl radicals (HRs). Since the AOP-SRs can effectively mineralize organics into carbon dioxide and water under the optimized operating conditions, they are used in the degradation of refractory organics such as dyes, pesticides, pharmaceuticals, and industrial additives. SRs can be produced by activating persulfate (PS) with ultraviolet, heat, ultrasound, microwave, transition metals, and carbon. The activation of PS in iron-based transition metals is widely studied because iron is an environmentally friendly and inexpensive material. This article reviews the mechanism and application of several iron-based materials, including ferrous iron (Fe2+), ferric iron (Fe3+), zero-valent iron (Fe0), nano-sized zero-valent iron (nFe0), materials-supported nFe0, and iron-containing compounds for PS activation to degrade refractory organics. In addition, the current challenges and perspectives of the practical application of PS activated by iron-based systems in wastewater treatment are analyzed and prospected.