Transition metal compounds demonstrated good performance in the removal of environmentally harmful contaminants, such as arsenic, while the aggregation propensity and poor chemical stability should be noticed. In this study, the nZVI/MXene@CNTs was adequately prepared by liquid reduction precipitation method for adsorption and oxidation of As(III) from the aqueous solution. The results of batch removal experiments showed that the maximum removal capacity of the nZVI/MXene@CNTs for As(III) was 443.32 mg/g with the pH = 3.0 at 25 °C. The effects of initial pH, dosage of materials and ionic strength on As(III) removal were explored. According to the various characterization analyses, the most plausible mechanisms of As(III) removal were the surface complexation, solid phase precipitation and the catalytic oxidation by the •OH. Furthermore, the nZVI/MXene@CNTs could be readily activated and reused via leaching with 0.1 M NaOH solution, due to the three-dimensional mesh intercalation structure. Therefore, it is a potential nanocomplex for removing and recovering As(III) from water with excellent capacity and environmental friendliness.