Due to increasingly serious water pollution problems, scientific researchers are constantly seeking state-of-the-art techniques for high-efficiency, cheap, user-friendly controlled, non-toxic water remediation. As a category of promising water treatment technology, Fenton-like oxidation is strongly limited by the sluggish kinetics of Fe(ii) recovery, however, zero valent iron (ZVI and Fe0) is an ideal sacrificial component to incessantly release Fe(ii) gauging the true potential of ZVI for continuable Fenton-like oxidation. This critical review systematically analyzes the reactivity of ZVI for oxidizing organic contaminants from the viewpoint of Fenton-like oxidation, involving coupling with peroxides (hydrogen peroxide, peroxydisulfate, and peroxymonosulfate), pH-dependent reactivity, the properties of various reactive oxygen species, simultaneous removal of heavy metals and organic contaminants, and application of ZVI-based Fenton-like systems to industrial wastewaters. Overall, the primary issue in promoting practical use of ZVI is the search for sustainable strategies to continuously corrode ZVI to release Fe(ii). In addition, we propose the technical and theoretical obstacles of ZVI-based Fenton-like oxidation for future studies. Although the current knowledge roadblocks were not totally removed, ZVI should be fearlessly used for water treatment, especially for industrial wastewater treatment.