Mesoporous zirconia nanostructures (MZN) were synthesized by hydrothermal method to efficiently remove highly mobile and toxic arsenite (As(III)) and arsenate (As(V)) from aqueous solutions. The as-synthesized MZN were characterized by Brunauer-Emmett-Teller (BET), X-Ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscope (HRTEM), and Energy-dispersive X-ray spectroscopy (EDX) techniques. The batch adsorption experimental results showed that the As(III) and As(V) removal capacities of the MZN were 105.03 and 110.29 mg/g, respectively, under neutral pH conditions, which were better than many recently reported adsorbents. The adsorption behavior of As(III) and As(V) on the MZN could be well described by pseudo-second-order and Langmuir isotherms models. Moreover, As(III) and As(V) adsorption on the MZN was spontaneous and endothermic. Some of the common co-existing ions had slightly affected the arsenic removal proficiency of MZN. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to investigate the adsorption mechanism of As(III) and As(V) on the as-synthesized MZN. The as-synthesized MZN demonstrated quite fast and good treatment of simulated real arsenic (As(III,V)) contaminated water. This study suggested that the as-synthesized MZN are potential candidate for practical applications of As(III) and As(V) removal from the aqueous solutions.