Nanoscale zero-valent iron (nZVI) has been extensively used for the passivation of cadmium (Cd) or arsenic (As) from wastewaters, while the underlying mechanisms of nZVI reaction with coexisting Cd and As are largely overlooked. Herein, the interactions of Cd and As during the course of nZVI transformation and the corresponding effects on respective pollutant removal have been systematically investigated. Batch experiments results show that As(III) addition significantly promotes the passivation of Cd(II) by nZVI, and the removal capacity increases by 7.8 times compared to that of Cd(II) alone. However, the adsorption and oxidative transformation of As(III) are barely affected under a relatively low Cd(II) concentration. It is conducive to the adsorption of Cd(II) and As(III) using nZVI under neutral conditions. The transformation of nZVI to lepidocrocite dominates in the Cd(II) single system, while it mainly converts to amorphous Fe oxyhydroxide with the addition of As(III). As(III) notably reduces the surface charge of Fe oxyhydroxide intermediates and to form the ternary complexes with Cd (Fe–As–Cd), which is the predominant mechanism for the promoted Cd(II) passivation. This work provides new understanding of nZVI transformation coupled to Cd(II) and As(III) passivation, which are likely contributing to the heavy metalloids regulation in waters and subsurface environments.