Arsenic pollution in drinking water or surface water has become a worldwide environmental issue and is a serious threat to human health. In this study, Mn-Fe-CO3 layered double hydroxides (LDHs) were prepared by the co-precipitation method, for the removal of As(III) and As(V) from solutions. The physical and chemical characteristics of LDHs were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). As(III) and As(V) adsorption capacities and the mechanism of metal removal by LDHs were determined by batch and column experiments. The results indicate that LDHs are novel and excellent adsorbents for arsenic removal.