In this study, the oxidation of 1-naphthol (1-NAP) and 2-naphthol (2-NAP) by Fe(VI) was investigated. The impacts of operating factors were investigated through a series of kinetic experiments, including Fe(VI) dosages, pH and coexisting ions (Ca2+, Mg2+, Cu2+, Fe3+, Cl−, SO42−, NO3− and CO32−). Almost 100% elimination of both 1-NAP and 2-NAP could be achieved within 300 s at pH 9.0 and 25 °C. Cu2+ could significantly improve the degradation efficiency of 1-NAP and 2-NAP, but the impacts of other ions were negligible. The liquid chromatography-mass spectrometry was used to identify the transformation products of 1-NAP and 2-NAP in Fe(VI) system, and the degradation pathways were proposed accordingly. Electron transfer mediated polymerization reaction was the dominant transformation pathway in the elimination of NAP by Fe(VI) oxidation. After 300 s of oxidation, heptamers and hexamers were found as the final coupling products during the removal of 1-NAP and 2-NAP, respectively. Theoretical calculations demonstrated that the hydrogen abstraction and electron transfer reaction would easily occur at the hydroxyl groups of 1-NAP and 2-NAP, producing NAP phenoxy radicals for subsequent coupling reaction. Moreover, since the electron transfer reactions between Fe(VI) and NAP molecules were barrierless and could occur spontaneously, the theoretical calculation results also confirmed the priority of coupling reaction in Fe(VI) system. This work indicated that the Fe(VI) oxidation was an effective way for removing naphthol, which may help us understand the reaction mechanism between phenolic compounds with Fe(VI). Display omitted •The oxidative removal of 1-NAP and 2-NAP by Fe(VI) was compared.•The transformation pathways of 1-NAP and 2-NAP were proposed.•Electron transfer-mediated polymerization was considered as the dominant pathway.•DFT calculated was conducted to prove the rationality of the reaction mechanisms.