Peanut-like hematite has been prepared by a new facile hydrothermal method and applied in the adsorption removal of As(V). The structural features of the as-prepared hematite were characterized systematically by X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller, scanning electron microscopy, energy-dispersive X-ray spectroscopy mapping, Fourier transform infrared spectroscopy, and transmission electron microscopy. Results showed that the morphologies of hematite could be tuned to spindle-like, oval-like, and cantaloupe-like shapes by adjusting the hydrothermal conditions. The peanut-like hematite formation followed a five-step route. At pH = 3, the adsorption amount of As(V) over peanut-like hematite reached 13.84 mg/g, and the adsorption kinetic process corresponded to the pseudo-second-order kinetic model. The peanut-like hematite also showed partial selectivity over As(V) in the hydrosphere. This method can be a reference for the preparation of other architectural metal oxide materials.